Ceria-based fluorite-like oxide solid solutions as catalysts of methane selective oxidation into syngas by the lattice oxygen: synthesis, characterization and performance

Садыков, В. А.; Кузнецова, Т. Г.; Alikina, G. M.; Frolova, Yu. V.; Lukashevich, Anton I.; Potapova, Yu.V.; Muzykantov, V.S.; Rogov, Vladimir A.; Kriventsov, V. V.; Кочубей, Д. И.; Мороз, Э. М.; Zyuzin, D.I.; Зайковский, В. И.; Kolomiichuk, V. N.; Паукштис, E. A.; Burgina, E. B.; Zyryanov, V. V.; Уваров, Н. Ф.; Neophytides, Stylianos G.; Kemnitz, Erhard

doi:10.1016/j.cattod.2004.05.016

Cited by 75 publications

(44 citation statements)

References 20 publications

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“…This is primary determined by a much higher reactivity of Pt atoms both for methane [7,22,23] and O 2 [10,34] activation, so the surface steps are mainly controlled by the Pt reactivity, while supports mainly affects the relaxation features. This is also provided by a much higher rate of the surface diffusion as compared with the bulk diffusion [34].…”

Section: Resultsmentioning

confidence: 99%

“…Complex oxides with fluorite-like structure, such as CeO 2 -ZrO 2 system doped by rare-earth cations (Gd, La, Sm, Pr) [7][8][9][10][11][12][13] are now among the most broadly studied catalysts and supports. Doping of ceria-zirconia solid solution and promotion by supported platinum group metals allow to tune the bonding strength, mobility and reactivity of oxygen [14,15].…”

Section: Introductionmentioning

confidence: 99%

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Effect of oxygen mobility in solid catalyst on transient regimes of catalytic reaction of methane partial oxidation at short contact times

et al. 2006

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Mathematical modeling of the effect of the oxygen mobility in a solid oxide catalyst on the dynamics of transients of fast catalytic reactions has been carried out. The analysis was based upon the redox mechanistic scheme with a due regard for diffusion of oxygen from the bulk of catalyst to its surface. Parameters of kinetic and mathematical models were selected via fitting of the experimental data for methane selective oxidation into syngas on 1.4%Pt/Gd 0.2 Ce 0.4 Zr 0.4 O x catalyst. The range of the Thiele parameter (/) where the oxygen bulk diffusion affects the most strongly reaction transients corresponds to /2[0:3 Ä 7]. For highsurface-area oxide catalysts, the bulk oxygen diffusion coefficients corresponding to this range of the Thiele parameter are in the range of10 À18 Ä 10 À13 cm 2 /s.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Effect of oxygen mobility in solid catalyst on transient regimes of catalytic reaction of methane partial oxidation at short contact times

et al. 2006

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“…For instance, an inverse correlation between lattice oxygen mobility and selectivity towards POM was observed for Ce 1Àx Gd x O 2Àd fluorite-type solid solutions [23]. Higher oxygen mobility in Ce 0:9 Sm 0:1 O 2Àd compared to that in Ce 0:45 Zr 0:45 La 0:10 O 2Àd [19] should promote the activation of oxygen ions at the platinum/ oxide interface and result in faster oxidation of methane and/or partial oxidation products. On the other hand, the instability of the Ce 0:45 Zr 0:45 La 0:10 O 2Àd cubic lattice, especially in the surface layers, is expected to increase the concentration of surface defects / active centers, thus improving the catalytic activity.…”

Section: Xrdmentioning

confidence: 93%

“…These ceria-based solid solutions were reported to exhibit significant catalytic activity for the oxidation of methane to synthesis gas by lattice oxygen [18,19]. Their catalytic activity can be further improved by modification of the surface with dispersed platinum, promoting methane dissociation and activation of lattice oxygen ions near the surface [18,19].…”

Section: Introductionmentioning

confidence: 97%

“…Ceria and its derivatives, exhibiting mixed oxygen-ionic and electronic conductivity under reducing conditions, provide an enlargement of the electrochemical reaction zone, reduction of anode polarization [6,[10][11][12][13], and continuous removal of carbon deposits due to oxygen storage/ release capacity [5,6,14]. In addition, ceria-based materials show substantial catalytic activity for partial oxidation of methane (POM), 1 2 O 2 þ CH 4 ) CO þ 2H 2 [14][15][16][17][18][19]. These components may, hence, promote selective electrochemical oxidation of methane directly on the SOFC anode (O 2À þ CH 4 ) CO þ 2H 2 þ 2e À Þ .…”

Section: Introductionmentioning

confidence: 99%

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Methane oxidation over nanocrystalline Ce0.45Zr0.45La0.10O2-δ/Pt and Ce0.9Sm0.1O2-δ/Pt anodes

et al. 2006

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The electrocatalytic activity of composite anodes, comprising metallic platinum and nanocrystalline Pt-modified Ce 0:45 Zr 0:45 La 0:10 O 2Àd and Ce 0:9 Sm 0:1 O 2Àd , was evaluated for the oxidation of dry methane in a solid oxide fuel cell (SOFC) -type reactor with yttria-stabilized zirconia solid electrolyte. At 923-1073 K, the total combustion is dominant, whilst above 1100 K the composite anodes exhibit significant catalytic activity towards the partial oxidation of methane (POM). At 1223 K and for a O 2 :CH 4 ratio equal to 0.5, stoichiometric for the POM reaction, CO selectivity and CH 4 conversion over Ce 0:9 Sm 0:1 O 2Àd /Pt achieves 55% and 41%, respectively. Under these conditions, Ce 0:45 Zr 0:45 La 0:10 O 2Àd /Pt anodes possess higher catalytic activity for partial oxidation, associated with the lower lattice oxygen mobility and instability of the Ce 0:45 Zr 0:45 La 0:10 O 2Àd cubic fluorite structure, and provide 54% conversion efficiency with 73% selectivity to carbon monoxide. Further increase in CH 4 conversion and CO selectivity can be achieved by packing the reactor with an additional catalyst, such as Pt-promoted Ce 0:45 Zr 0:45 La 0:10 O 2Àd or LaNiO 3Àd =Al 2 O 3 .

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Oxide Solid Solutions

Cimino

Stone

2008

Handbook of Heterogeneous Catalysis

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The sections in this article are Introduction Principles, Preparation, and Characterization Principles Preparation Characterization Bulk Composition and Structure Surface Composition Catalysis in the Context of Activity N 2 O Decomposition, CO Oxidation and H 2  D 2 Equilibration Combustion of Hydrocarbons Perovskite Catalysts Hexa‐Aluminate Catalysts Ceria‐Containing Catalysts Catalysis in the Context of Selectivity Selective Oxidation Reactions Involving Dehydrogenation, Hydrogenation, and Reforming Catalysis in the Context of Surface Acidity and Basicity Dehydration of Alcohols on Ionic Solid Solutions Acid Catalysis by Aluminophosphates Conclusions

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Ceria-based fluorite-like oxide solid solutions as catalysts of methane selective oxidation into syngas by the lattice oxygen: synthesis, characterization and performance

Cited by 75 publications

References 20 publications

Effect of oxygen mobility in solid catalyst on transient regimes of catalytic reaction of methane partial oxidation at short contact times

Effect of oxygen mobility in solid catalyst on transient regimes of catalytic reaction of methane partial oxidation at short contact times

Methane oxidation over nanocrystalline Ce0.45Zr0.45La0.10O2-δ/Pt and Ce0.9Sm0.1O2-δ/Pt anodes

Oxide Solid Solutions

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