Bulk transport and oxygen surface exchange of the mixed ionic electronic conductor Ce1-xTbxO2-δ (x= 1⁄4, 0.1, 0.2, 0.5)

Bulk ionic and electronic transport properties and the rate of oxygen surface exchange of Tb-doped ceria have been evaluated as a function of Tb concentration, aiming to assess the potential use of the materials as high-temperature oxygen-transport membranes and oxygen reduction catalysts. The materials were synthesized by the co-precipitation method. Cobalt oxide (2 mol%) was added in order to improve sinterability and conductivity. The materials were studied by means of X-ray diffraction (XRD), temperatureprogrammed desorption (TPD), thermogravimetry (TG), DC-conductivity and UV-vis spectrophotometry. The results indicate that the extent of mixed ionic–electronic conductivity is a function of temperature and can be tuned by modifying the Tb- (and Co-doping) concentration. Low Tb-content materials (x ¼ 0.1 and 0.2) are predominant ionic conductors, but the materials with 50 mol% Tb show both p-type electronic and ionic conductivity. The enhanced electronic conduction in Ce0.5Tb0.5O2 d is associated with narrowing of the band gap upon doping ceria with Tb. In addition, the surface chemistry of the samples was investigated by means of X-ray photoelectron spectroscopy (XPS) and pulse isotopic exchange (PIE). The surface exchange rate is found to increase on increasing the level of Tb doping. The highest surface exchange rates in this study are found for materials doped with 50 mol% Tb.

[1]  J. M. Serra,et al.  Rare Earth‐doped Ceria Catalysts for ODHE Reaction in a Catalytic Modified MIEC Membrane Reactor , 2012 .

[2]  S. Bishop,et al.  Praseodymium doped ceria: Model mixed ionic electronic conductor with coupled electrical, optical, mechanical and chemical properties , 2012 .

[3]  J. M. Serra,et al.  Combined investigation of bulk diffusion and surface exchange parameters of silver catalyst coated yttrium-doped BSCF membranes. , 2012, Physical chemistry chemical physics : PCCP.

[4]  J. M. Serra,et al.  Structural–Transport Properties Relationships on Ce1–xLnxO2−δ System (Ln = Gd, La, Tb, Pr, Eu, Er, Yb, Nd) and Effect of Cobalt Addition , 2012 .

[5]  M. J. Cocero,et al.  Cobalt oxide nanoparticles on mesoporous MCM-41 and Al-MCM-41 by supercritical CO2 deposition , 2012 .

[6]  J. M. Serra,et al.  On the Use of Supported Ceria Membranes for Oxyfuel process / Syngas Production , 2011 .

[7]  H. Swart,et al.  Low voltage electron induced cathodoluminescence degradation and surface characterization of Sr3(PO4)2:Tb phosphor , 2011 .

[8]  José M. Serra,et al.  Ultrahigh oxygen permeation flux through supported Ba0.5Sr0.5Co0.8Fe0.2O3−δ membranes , 2011 .

[9]  E. Wachsman,et al.  Determination of Surface Exchange Coefficients of LSM, LSCF, YSZ, GDC Constituent Materials in Composite SOFC Cathodes , 2011 .

[10]  Lakshmi Katta,et al.  Nanosized Unsupported and Alumina-Supported Ceria-Zirconia and Ceria-Terbia Solid Solutions for CO Oxidation , 2011 .

[11]  J. M. Serra,et al.  Study of the Transport Properties of the Mixed Ionic Electronic Conductor Ce1−xTbxO2−δ + Co (x = 0.1, 0.2) and Evaluation As Oxygen-Transport Membrane , 2011 .

[12]  Shaomin Liu,et al.  High performance perovskite hollow fibres for oxygen separation , 2011 .

[13]  E. Paparazzo.  On the curve-fitting of XPS Ce(3d) spectra of cerium oxides , 2011 .

[14]  M. Janssen,et al.  Electronic conductivity of Ce0.8Gd0.2−xPrxO2−δ and influence of added CoO , 2011 .

[15]  B. Boukamp,et al.  Oxygen surface exchange kinetics of erbia-stabilized bismuth oxide , 2011 .

[16]  K. Efimov,et al.  CO2-stable and cobalt-free dual-phase membrane for oxygen separation. , 2011, Angewandte Chemie.

[17]  P. A. Jensen,et al.  Oxy-fuel combustion of solid fuels , 2010 .

[18]  B. Boukamp,et al.  A novel pulse isotopic exchange technique for rapid determination of the oxygen surface exchange rate of oxide ion conductors. , 2009, Physical chemistry chemical physics : PCCP.

[19]  Amit Kumar,et al.  Luminescence properties of europium-doped cerium oxide nanoparticles: role of vacancy and oxidation states. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[20]  Shaomin Liu,et al.  Development of mixed conducting membranes for clean coal energy delivery , 2009 .

[21]  Jung Hoon Park,et al.  Oxygen permeation and stability of Ba0.5Sr0.5Co0.8Fe0.2O3−δ membrane according to trace elements and oxygen partial pressure in synthetic air , 2009 .

[22]  D. P. Fagg,et al.  Transport Properties of Fluorite-Type Ce0.8Pr0.2O2−δ: Optimization via the Use of Cobalt Oxide Sintering Aid , 2009 .

[23]  A. Hagen,et al.  Oxygen Nonstoichiometry and Defect Chemistry Modelling of Ce0.8PrxTb0.2-xO2-δ , 2008 .

[24]  Jaka Sunarso,et al.  Mixed ionic-electronic conducting (MIEC) ceramic-based membranes for oxygen separation , 2008 .

[25]  Chen-Bin Wang,et al.  Characterization of cobalt oxides studied by FT-IR, Raman, TPR and TG-MS , 2008 .

[26]  J. M. Serra,et al.  IT-SOFC supported on Mixed Oxygen Ionic-Electronic Conducting Composites , 2008 .

[27]  A. Murphy.  Band-gap determination from diffuse reflectance measurements of semiconductor films, and application to photoelectrochemical water-splitting , 2007 .

[28]  M. Mogensen,et al.  Effects of firing schedule on solubility limits and transport properties of ZrO2–TiO2–Y2O3 fluorites , 2007 .

[29]  D. P. Fagg,et al.  High oxygen permeability in fluorite-type Ce0.8Pr0.2O2−δ via the use of sintering aids , 2007 .

[30]  L. C. Jonghe,et al.  Prediction and evaluation of sintering aids for Cerium Gadolinium Oxide , 2007 .

[31]  J. Zou,et al.  Microstructural characterization of terbium-doped ceria , 2007 .

[32]  A. Feldhoff,et al.  Influence of CO2 on the oxygen permeation performance and the microstructure of perovskite-type (Ba0.5Sr0.5)(Co0.8Fe0.2)O3−δ membranes , 2007 .

[33]  R. Bredesen,et al.  Dense ceramic membranes based on ion conducting oxides , 2007 .

[34]  X. Tan,et al.  Oxygen production using dense ceramic hollow fiber membrane modules with different operating modes , 2007 .

[35]  E. Wachsman,et al.  The role of point defects in the physical properties of nonstoichiometric ceria , 2007 .

[36]  D. P. Fagg,et al.  Oxygen permeability, thermal expansion and mixed conductivity of GdxCe0.8-xPr0.2O2-δ, x = 0, 0.15, 0.2 , 2006 .

[37]  Zongping Shao,et al.  Ba0.5Sr0.5Co0.8Fe0.2O3-δ ceramic hollow-fiber membranes for oxygen permeation , 2006 .

[38]  B. Boukamp,et al.  Oxygen transport in La0.6Sr0.4Co1−yFeyO3−δ , 2004 .

[39]  H. Yokokawa,et al.  Mass transport properties of Ce0.9Gd0.1O2−δ at the surface and in the bulk , 2002 .

[40]  A. Galtayries,et al.  Influence of the nature of the noble metal (Rh,Pt) on the low‐temperature reducibility of a Ce/Tb mixed oxide with application as TWC component , 2002 .

[41]  F. Larachi,et al.  Ce 3d XPS study of composite CexMn1 xO2 y wet oxidation catalysts , 2002 .

[42]  J. Kilner,et al.  Oxygen surface exchange on gadolinia doped ceria , 2000 .

[43]  Zongping Shao,et al.  Investigation of the permeation behavior and stability of a Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxygen membrane , 2000 .

[44]  A. Virkar,et al.  Lattice Parameters and Densities of Rare‐Earth Oxide Doped Ceria Electrolytes , 1995 .

[45]  L. Guczi,et al.  Structure and catalytic activity of alumina supported platinum-cobalt bimetallic catalysts. 3. Effect of treatment on the interface layer , 1992 .

[46]  R. López,et al.  Band-gap energy estimation from diffuse reflectance measurements on sol–gel and commercial TiO2: a comparative study , 2011, Journal of Sol-Gel Science and Technology.

[47]  J. Bassat,et al.  Chemical oxygen diffusion coefficient measurement by conductivity relaxation—correlation between tracer diffusion coefficient and chemical diffusion coefficient , 2004 .

[48]  C. Rao,et al.  XPES studies of oxides of second- and third-row transition metals including rare earths , 1980 .