Reduction of CeO<sub>2</sub> in composites with transition metal complex oxides under hydrogen containing atmosphere and its correlation with catalytic activity

doi:10.1007/s11705-013-1333-6

Front Chem Sci Eng

2013, Vol. 7

Issue (3) : 249-261 https://doi.org/10.1007/s11705-013-1333-6

RESEARCH ARTICLE

Reduction of CeO₂ in composites with transition metal complex oxides under hydrogen containing atmosphere and its correlation with catalytic activity

Elena Yu. KONYSHEVA^1,2(

)

1. School of Chemistry, University of St Andrews, KY169ST, St Andrews, Fife, UK; 2. Department of Chemistry, Xi'an Jiaotong-Liverpool University, Suzhou 215123, China

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Abstract

Reduction behavior of pure and doped CeO₂, the multi-phase La_0.6Sr_0.4CoO₃?xCeO₂, La_0.8Sr_0.2MnO₃ ?xCeO₂, and La_0.95Ni_0.6Fe_0.4O₃?xCeO₂ composites, was studied under hydrogen containing atmosphere to address issues related to the improvement of electrochemical and catalytic performance of electrodes in fuel cells. The enhanced reduction of cerium oxide was observed initially at 800°C in all composites in spite of the presence of highly reducible transition metal cations that could lead to the increase in surface concentration of oxygen vacancies and generation of the electron enriched surface. Due to continuous reduction of cerium oxide in La_0.6Sr_0.4CoO₃?xCeO₂ and La_0.8Sr_0.2MnO₃?xCeO₂ (up to 10 h) composites the redox activity of the Ce⁴⁺/Ce³⁺ pair could be suppressed and additional measures are required for reversible spontaneous regeneration of Ce⁴⁺. After 3 h exposure to H₂-Ar at 800°C the reduction of cerium oxides and perovskite phases in La_0.95Ni_0.6Fe_0.4O₃?xCeO₂ composites was diminished. The extent of cerium oxide involvement in the reduction process varies with time, and depends on its initial deviation from oxygen stoichiometry (that results in the larger lattice parameter and the longer pathway for O^2- transport through the fluorite lattice), chemical origin of transition metal cations in the perovskite, and phase diversity in multi-phase composites.

Keywords reduction of cerium oxide composites perovskites catalyst under hydrogen containing atmosphere

Corresponding Author(s): KONYSHEVA Elena Yu.,Email:elena.konysheva@googlemail.com, elena.konysheva@xjtlu.edu.cn

Issue Date: 05 September 2013

Cite this article:

Elena Yu. KONYSHEVA. Reduction of CeO₂ in composites with transition metal complex oxides under hydrogen containing atmosphere and its correlation with catalytic activity[J]. Front Chem Sci Eng, 2013, 7(3): 249-261.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-013-1333-6
https://academic.hep.com.cn/fcse/EN/Y2013/V7/I3/249

Fig.1 (a) Relative weight change of single phase compounds with fluorite structure at 800°C under H-Ar atmosphere and (b) experimental data from Fig. 1(a) are plotted as “” “time”, where α is the conversion fraction. 1. CeO; 2. CeLaSrCoO

Fig.2 XRD patterns of CeO initially and after exposure to H-Ar atmosphere at 800°C for 10 h

Tab.1 Surface atomic composition derived from XPS for pure and multi-cation doped cerium oxides with fluorite structure calcined at 1350°C for 5 h in air

Fig.3 Curve-fitted Ce3 core level spectrum of CeLaSrCoO

Fig.4 Mass change and thermo-effects observed during reduction of (a) LaSrCoO (LSC) perovskite, LSCC25 and LSCC57 composites; and (b) LNFC02 and LNFC57 composites. TEf1 and TEf2 stand for the 1 and 2 exothermic effects, respectively

Fig.5 (a) –(c) Reduction of the LSCC, LSMC, and LNFC composites during exposure to H-Ar at 800°C. The borders between stages I, II, and III are marked on figures conditionally. TGA data are presented after the subtraction of the corrections; (d) –(f) XPD patterns of LSCC25, LSMC25, and LNFC25 composites initially and after reduction under H-Ar atmosphere at 800°C

Fig.6 Compositional dependences of the weight loss in the LSCC, LSMC, and LNFC series after (a,b) 0.4 h, (c) 1.2 h, (d) 3 h, (e) 5.5 h, and (f) 8 h. Comparison of (1) the expected weight loss if only transition metal cations from perovskites contribute to the reduction of composites (data are marked as dot lines), (2) the expected weight loss due to the simultaneous reduction of transition metal cations in perovskites and Ce cations in CeO in proportions corresponding to their fractions in the composites (data are marked as dash-dot lines), and (3) the experimental data obtained in TGA experiments under H-Ar atmosphere at 800°C (data are marked as solid lines with symbols). Error bars are within the symbols

Fig.7 Room temperature lattice parameter of the modified cerium oxides with fluorite structure in the LSCC, LSMC, and LNFC composites fabricated under air at 1350°C. Data for the LNFC composites are presented for both main and minor fraction of modified cerium oxide

1	Voorhoeve R J H, Remeika J P, Freeland P E, Matthias B T. Rare-earth oxides of manganese and cobalt rival platinum for the treatment of carbon monoxide in auto exhaust. Science , 1972, 177(4046): 353–354 doi: 10.1126/science.177.4046.353
2	Trovarelli A. Catalytic properties of ceria and CeO₂-containing materials. Catalysis Reviews. Science and Engineering , 1996, 38(4): 439–520 doi: 10.1080/01614949608006464
3	Lombardo E A, Ulla M A. Perovskite oxides in catalysis: past, present and future. Research on Chemical Intermediates , 1998, 24(5): 581–592 doi: 10.1163/156856798X00104
4	Sin A, Kopnin E, Dubitsky Y, Zaopo A, Aricò A S, Gullo L R, La Rosa D, Antonucci V J. Stabilisation of composite LSFCO-CGO based anodes for methane oxidation in solid oxide fuel cells. Journal of Power Sources , 2005, 145(1): 68–73 doi: 10.1016/j.jpowsour.2004.12.040
5	Ferri D. NO reduction by H₂ over perovskite-like mixed oxides. Catal. B: Environmental , 1998, 16(4): 339–345 doi: 10.1016/S0926-3373(97)00090-8
6	Falcon H, Carbonio R E, Fierro J L G. Correlation of Oxidation States in LaFe_xNi_1-xO_3+δ oxides with catalytic activity for H₂O₂ decomposition. Catalysis , 2001, 203(2): 264–272 doi: 10.1006/jcat.2001.3351
7	Petunchi J O, Nicastro J L, Lombardo E A J. Ethylene hydrogenation over LaCoO₃ perovskite. Journal of the Chemical Society. Chemical Communications , 1980, 1980(11): 467–468 doi: 10.1039/c39800000467
8	Cheng D G, Chong M, Chen F, Zhan X. XPS Characterization of CeO₂ catalyst for hydrogenation of benzoic acid to benzaldehyde. Catalysis Letters , 2008, 120(1): 82–85 doi: 10.1007/s10562-007-9252-0
9	Gross M D, Vohs J M, Gorte R J. A strategy for achieving high performance with SOFC ceramic anodes. Electrochemical and Solid-State Letters , 2007, 10(4): B65–B69 doi: 10.1149/1.2432942
10	Gross M D, Vohs J M, Gorte R J. An examination of SOFC anode functional layers based on ceria in YSZ. Journal of the Electrochemical Society , 2007, 154(7): B694–B699 doi: 10.1149/1.2736647
11	Wang S, Kato T, Nagata S, Honda T, Kaneko T, Iwashita N, Dokiya M. Ni/Ceria cermet as anode of reduced-temperature solid oxide fuel cells. Journal of the Electrochemical Society , 2002, 149(7): A927–A933 doi: 10.1149/1.1483867
12	Huang Y H, Dass R I, Xing Z L, Goodenough J B. Double perovskites as anode materials for solid-oxide fuel cells. Science , 2006, 312(5771): 254–257 doi: 10.1126/science.1125877
13	Tao S W, Irvine J T S. A redox-stable efficient anode for solid-oxide fuel cells. Nature Materials , 2003, 2(5): 320–323 doi: 10.1038/nmat871
14	Kim G, Corre G, Irvine J T S, Vohs J M, Gorte R J. Engineering composite oxide SOFC anodes for efficient oxidation of methane. Electrochemical and Solid-State Letters , 2008, 11(2): B16–B19 doi: 10.1149/1.2817809
15	Cordatos H, Gorte R J C O. NO, and H₂ adsorption on ceria-supported Pd. Catalysis , 1996, 159(1): 112–118 doi: 10.1006/jcat.1996.0070
16	Nakamura T, Petzow G, Gauckler L J. Stability of the perovskite phase LaBO₃ (B= V, Cr, Mn, Fe, Co, Ni) in reducing atmosphere I. Experimental results. Materials Research Bulletin , 1979, 14(5): 649–659 doi: 10.1016/0025-5408(79)90048-5
17	Radovic M, Speakman S A, Allard L F, Payzant E A, Lara-Curzio E, Kriven W M, Lloyd J, Fegely L, Orlovskaya N. Thermal, mechanical and phase stability of LaCoO₃ in reducing and oxidizing environments. Journal of Power Sources , 2008, 184(1): 77–83 doi: 10.1016/j.jpowsour.2008.05.063
18	Konysheva E, Irvine J T S. Evolution of conductivity, structure and thermochemical stability of lanthanum manganese iron nickelate perovskites. Journal of Materials Chemistry , 2008, 18(42): 5147–5154 doi: 10.1039/b807145d
19	Konysheva E, Irvine J T S. Thermochemical and structural stability of A- and B-site-substituted perovskites in hydrogen-containing atmosphere. Chemistry of Materials , 2009, 21(8): 1514–1523 doi: 10.1021/cm802996p
20	Konysheva E, Suard E, Irvine J T S. Effect of oxygen non stoichiometry and oxidation state of transition elements on high-temperature phase transition in a-site deficient La₀.₉₅Ni₀.₆Fe₀.₄O_3-δ perovskite. Chemistry of Materials , 2009, 21(21): 5307–5318 doi: 10.1021/cm902443n
21	Konysheva E, Irvine J T S. In situ high-temperature neutron diffraction study of A-site deficient perovskites with transition metals on the B-sublattice and structure-conductivity correlation. Chemistry of Materials , 2011, 23(7): 1841–1850 doi: 10.1021/cm103486z
22	Teraoka Y, Nobunaga T, Okamoto K, Miura N, Yamazoe N. Influence of constituent metal cations in substituted LaCoO₃ on mixed conductivity and oxygen permeability. Solid State Ionics , 1991, 48(3-4): 207–212 doi: 10.1016/0167-2738(91)90034-9
23	Ishigaki T, Yamauchi S, Mizusaki J, Fueki K, Tamura H. Tracer diffusion coefficient of oxide ions in LaCoO₃ single crystal. Journal of Solid State Chemistry , 1984, 54(1): 100–107 doi: 10.1016/0022-4596(84)90136-1
24	Ishigaki T, Yamauchi S, Kishio K, Mizusaki J, Fueki K. Diffusion of oxide ion vacancies in perovskite-type oxides. Journal of Solid State Chemistry , 1988, 73(1): 179–187 doi: 10.1016/0022-4596(88)90067-9
25	Hayward M A, Cussen E J, Claridge J B, Bieringer M, Rosseinsky M J, Kiely C J, Blundell S J, Marshall I M, Pratt F L. The hydride anion in an extended transition metal oxide array: LaSrCoO₃H₀.7. Science , 2002, 295(5561): 1882–1884 doi: 10.1126/science.1068321
26	Bridges C A, Darling G R, Hayward M A, Rosseinsky M J. Electronic structure, magnetic ordering, and formation pathway of the transition metal oxide hydride LaSrCoO₃H₀.7. Journal of the American Chemical Society , 2005, 127(16): 5996–6011 doi: 10.1021/ja042683e
27	Rietveld H M. A profile refinement method for nuclear and magnetic structures. Journal of Applied Crystallography , 1969, 2(2): 65–71 doi: 10.1107/S0021889869006558
28	Sayle T X T, Parker S C, Catlow C R A. Surface oxygen vacancy formation on CeO₂ and its role in the oxidation of carbon monoxide. Journal of the Chemical Society. Chemical Communications , 1992, 1992(14): 977–978 doi: 10.1039/c39920000977
29	Yang Z, Yu X, Lu Z, Li S, Hermansson K. Oxygen vacancy pairs on CeO₂ (110): A DFT+U study. Physics Letters. [Part A] , 2009, 373(31): 2786–2792 doi: 10.1016/j.physleta.2009.05.055
30	Tuller H L, Nowick A S. Small polaron electron transport in reduced CeO₂ single crystals. Journal of Physics and Chemistry of Solids , 1977, 38(8): 859–867 doi: 10.1016/0022-3697(77)90124-X
31	Tuller H L, Nowick A S. Defect structure and electrical properties of nonstoichiometric CeO₂ single crystals. Journal of the Electrochemical Society , 1979, 126(2): 209–217 doi: 10.1149/1.2129007
32	Blumental R N, Sharma R K. Electronic conductivity in nonstoichiometric cerium dioxide. Journal of Solid State Chemistry , 1975, 13(4): 360–364 doi: 10.1016/0022-4596(75)90152-8
33	Hull S, Norberg S T, Ahmed I, Eriksson S G, Marrocchelli D, Madden P A. Oxygen vacancy ordering within anion-deficient ceria. Journal of Solid State Chemistry , 2009, 182(10): 2815–2821 doi: 10.1016/j.jssc.2009.07.044
34	Tsch?pe A, Sommer E, Birringer R. Grain size-dependent electrical conductivity of polycrystalline cerium oxide. I. Experiments. Solid State Ionics , 2001, 139(3-4): 255–265 doi: 10.1016/S0167-2738(01)00678-6
35	Tsch?pe A, Birringer R. Grain size dependence of electrical conductivity in polycrystalline cerium oxide. Journal of Electroceramics , 2001, 7(3): 169–177 doi: 10.1023/A:1014483028210
36	Gao P, Kang Z, Fu W, Wang W, Bai X, Wang E. Electrically driven redox process in cerium oxides. Journal of the American Chemical Society , 2010, 132(12): 4197–4201 doi: 10.1021/ja9086616
37	Laachir A, Perrichon V, Badri A, Lamotte J, Catherine E, Lavalley J C, Fallah J E, Hilaire L, Normand F L, Quéméré E, Sauvion G N, Touret O. Reduction of CeO₂ by hydrogen. Magnetic susceptibility and fourier-transform infrared, ultraviolet and X-ray photoelectron spectroscopy measurements. Journal of the Chemical Society, Faraday Transactions , 1991, 87(10): 1601–1609 doi: 10.1039/ft9918701601
38	Konysheva E, Irvine J T S. Transport properties of multi-cations doped cerium oxide. Solid State Ionics , 2011, 184(1): 27–30 doi: 10.1016/j.ssi.2010.09.032
39	?atava V, ?kvara F. Mechanism and kinetics of the decomposition of solids by a thermogravimetric method. Journal of the American Ceramic Society , 1969, 52(11): 591–595 doi: 10.1111/j.1151-2916.1969.tb15846.x
40	Khawam A, Flanagan D R. Solid-state kinetic models: Basics and mathematical fundamentals. Journal of Physical Chemistry B , 2006, 110(35): 17315–17328 doi: 10.1021/jp062746a
41	Yamamura H, Katoh E, Ichikawa M, Kakinuma K, Mori T, Haneda H. Multiple doping effect on the electrical conductivity in the (Ce_1-x-yLa_xMy)O_2-δ (M= Ca, Sr) system. Electrochemistry , 2000, 68(6): 455–459
42	Zuev A, Singheiser L, Hilpert K. Oxygen vacancy formation and defect structure of Cu-doped lanthanum chromite LaCr₀.79Cu₀.05Al₀.16O_3-δ. Solid State Ionics , 2005, 176(3-4): 417–421 doi: 10.1016/j.ssi.2004.08.003
43	Petrov A N, Zuev A Yu, Vylkov A I, Tsvetkov D S. Defect structure and charge transfer in undoped and doped lanthanum cobaltites. Journal of Materials Science , 2007, 42(6): 1909–1914 doi: 10.1007/s10853-006-0346-7
44	Zhang F, Wang P, Koberstein J, Khalid S, Chan S W. Cerium oxidation state in ceria nanoparticles studied with X-ray photoelectron spectroscopy and absorption near edge spectroscopy. Surface Science , 2004, 563(1): 74–82 doi: 10.1016/j.susc.2004.05.138
45	Konysheva E Yu, Francis S M. Identification of surface composition and chemical states in composites comprised of phases with fluorite and perovskite structures by X-ray photoelectron spectroscopy. Applied Surface Science , 2013, 268(1): 278–287 doi: 10.1016/j.apsusc.2012.12.079
46	Shannon R D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica. Section A, Foundations of Crystallography , 1976, 32(5): 751–767 doi: 10.1107/S0567739476001551
47	Konysheva E Yu, Francis S M, Irvine J T S, Rolle A, Vannier R N. Red-ox behaviour in the La₀.6Sr₀.4CoO_3±δ-CeO₂ system. Journal of Materials Chemistry , 2011, 21(39): 15511–15520 doi: 10.1039/c1jm12582f
48	JCPDS, International Centre for Diffraction Data, file No. 34-0394
49	Konysheva E, Francis S M, Irvine J T S. Crystal structure, oxygen nonstoichiometry, and conductivity of mixed ionic-electronic conducting perovskite composites with CeO₂. Journal of the Electrochemical Society , 2010, 157(1): B159–B165 doi: 10.1149/1.3256117
50	Konysheva E, Irvine J T S, Besmehn A. Crystal structure, thermochemical stability, electrical and magnetic properties of the two-phase composites in the La₀.8Sr₀.2MnO_3±δ-CeO₂ system. Solid State Ionics , 2009, 180(11-13): 778–783 doi: 10.1016/j.ssi.2008.12.027
51	Poulsen F W. Defect chemistry modelling of oxygen-stoichiometry, vacancy concentrations, and conductivity of (La_1-xSr_x)MnO_3±δ. Solid State Ionics , 2000, 129(1-4): 145–162 doi: 10.1016/S0167-2738(99)00322-7
52	Konysheva E, Irvine J T S. The La₀.95Ni₀.6Fe₀.4O₃-CeO₂ system: phase equilibria, crystal structure of components and transport properties. Journal of Solid State Chemistry , 2011, 184(6): 1499–1504 doi: 10.1016/j.jssc.2011.04.027
53	Pound B G. The characterization of doped CeO₂ electrodes in solid oxide fuel cells. Solid State Ionics , 1992, 52(1): 183–188 doi: 10.1016/0167-2738(92)90104-W
54	Belov B F, Goroh A V, Demchuk V P, Dorschenko N A, Somojlenko Z A. Inorganic Materials , 1983, 19(3): 231–234
55	Robbins M, Wertheim G K, Menth A, Sherwood R C. Preparation and properties of polycrystalline cerium orthoferrite (CeFeO₃). Journal of Physics and Chemistry of Solids , 1969, 30(7): 1823–1825 doi: 10.1016/0022-3697(69)90250-9

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