Density functional theory study on oxygen adsorption in LaSrCoO4: An extended cathode material for solid oxide fuel cells

Zhou, Jun; Chen, Gang; Wu, Kai; Cheng, Yonghong; Peng, Bo; Guo, J.; Jiang, Yizhe

doi:10.1016/j.apsusc.2011.11.050

Cited by 23 publications

(7 citation statements)

References 39 publications

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“…Convergence with respect to k -point sampling, kinetic energy cutoff, and slab thickness was tested and found to be satisfactory. The geometry of the isolated O 2 molecule was optimized using a large cubic cell of 8 Å × 8 Å × 8 Å, similar to previous study . The predicted O–O bond length was equal to 1.24 Å and was in good agreement with the experimental values of 1.21 Å.…”

Section: Computational Details and Surface Configurationssupporting

confidence: 67%

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Interaction of La₂NiO₄ (100) Surface with Oxygen Molecule: A First-Principles Study

Zhou

Chen

et al. 2013

J. Phys. Chem. C

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Along the way to designing of new cathode materials for solid oxide fuel cells (SOFCs), an understanding of the mechanism of oxygen reduction reaction (ORR) plays a key role, especially the interaction between O 2 molecule and surface of cathode. Recently, La 2 NiO 4 with K 2 NiF 4 -type structure has been developed, and it has received great attention as an oxygen sensor and a potential cathode for SOFCs. However, the chemical activity of La 2 NiO 4 , in particular, the ORR on the surface, has not been studied so thoroughly. In this report, we present the structural and energetic results of O 2 adsorbed onto the perfect and defective La 2 NiO 4 (100) surface to elucidate the interaction mechanism between O 2 molecule and cathode using atomistic computer simulation based on density functional theory. The results show that the surface structure and the adsorbed configurations are vital for O 2 adsorption. and activation. The adsorbed species on the perfect surface are energetically less favorable than defective surface. The Ni site is preferred with adsorption energy of −1.25 (Ni-super) and −1.80 eV (Ni-per), much higher than these of La site, supporting the fact that transition-metal cations are more active than lanthanon metals in K 2 NiF 4 -type compounds. Surface oxygen vacancy is found to enhance the adsorption energy of O 2 molecule on the La 2 NiO 4 (100) surface; in addition, oxygen vacancy can be an active site in O 2 adsorption. The most stable configuration is Ni−O−Ni mode, with the highest adsorption energy being −2.61 eV. This can be confirmed by the analysis of the local density of states (LDOS) and the difference electron density. These results have an important implication for understanding the ORR on La 2 NiO 4 (100) surface.

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Section: Computational Details and Surface Configurationssupporting

confidence: 67%

“…The geometry of the isolated O 2 molecule was optimized using a large cubic cell of 8 Å × 8 Å × 8 Å, similar to previous study. 41 The predicted O−O bond length was equal to 1.24 Å and was in good agreement with the experimental values of 1.21 Å. The calculated binding energy of free O 2 molecule is 6.52 eV.…”

Section: Computational Details and Surfacementioning

confidence: 99%

Interaction of La₂NiO₄ (100) Surface with Oxygen Molecule: A First-Principles Study

Zhou

Chen

et al. 2013

J. Phys. Chem. C

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“…In this case the O 2 reduction was calculated to be more energetically favourable on Co sites (B-sites) than on La/Sr sites (A-sites), on the basis of the difference in adsorption energies. 14 Furthermore, DFT simulations on single perovskite LaMnO 3 (001) surfaces predict the cubic MnO 2 surface (B-site) with adsorbed O atoms to be the most stable one 15 and ab initio studies on several perovskite SOFC cathode materials (LaBO 3 (001) with B]Mn, Fe, Co and Ni) suggest the LaO (A-site) termination to be catalytically inactive due to its high O vacancy formation and strong O adsorption energies. 16 Typically surfaces are difficult to analyze due to their sensitivity to carbonation, and the issue of segregation of species to outermost layers.…”

Section: Broader Contextmentioning

confidence: 99%

Absence of Ni on the outer surface of Sr doped La₂NiO₄single crystals

Burriel

Wilkins

Hill

et al. 2014

Energy Environ. Sci.

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“…61 It is acceptable to use DFT-GGA/PBE or DFT-GGA/PW91 to describe the interactions between the gas molecule (including CO 2 ) and the La based perovskite (ABO 3 structure, including LaFeO 3 ) and related compounds (such as the K 2 NiF 4 structure). 26,35,[57][58][59][62][63][64][65][66][67][68][69] With an increase of RH, the resistance of sensor decreases, similar to other kinds of semiconducting-oxide sensors. [36][37][38][39][40][41][42][43][44][45][46] At room temperature, the physisorbed water layer usually appears, the conduction is dominated by the Grotthuss mechanism, where the proton H + or H 3 O + dissociated from water may have more and more freedom to move inside of the condensed water layer with an increase of RH, leading to the reduction of resistance.…”

Section: Calculation Methods and Modelsmentioning

confidence: 58%

CO₂ sensing of La_0.875Ca_0.125FeO₃ in wet vapor: a comparison of experimental results and first-principles calculations

Chen

Qin

et al. 2015

Phys. Chem. Chem. Phys.

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Experimental results show that with an increase of relative humidity, the resistance of La0.875Ca0.125FeO3 decreases at room temperature but increases at higher temperatures (140-360 °C). The humid effect at room temperature is due to the movement of H(+) or H3O(+) inside of the condensed water layer on the surface of La0.875Ca0.125FeO3. Regarding the humid effect at high temperatures, the density functional theory (DFT) calculations show that H2O can be adsorbed onto the La0.875Ca0.125FeO3 surface in the molecular and dissociative adsorption configurations, where the La0.875Ca0.125FeO3 surface gains some electrons from H2O or its dissociative products, consistent with our observation. Experimental results also show that CO2 sensing response at high temperatures decreases with an increase of room-temperature relative humidity. DFT calculations indicate that CO2 adsorbed onto the La0.875Ca0.125FeO3(010) surface, where high concentration oxygen adsorption occurs without water adsorption nearby, releases some electrons into the semiconductor surface, playing the role of a donor. The interaction between CO2 and the local La0.875Ca0.125FeO3(010) surface with pre-adsorption of H2O nearby results in some electron transfer from the La0.875Ca0.125FeO3 surface to CO2, which is responsible for the weakening of CO2 response at high temperatures for La0.875Ca0.125FeO3 with an increase of room-temperature relative humidity.

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Density functional theory study on oxygen adsorption in LaSrCoO4: An extended cathode material for solid oxide fuel cells

Cited by 23 publications

References 39 publications

Interaction of La₂NiO₄ (100) Surface with Oxygen Molecule: A First-Principles Study

Interaction of La₂NiO₄ (100) Surface with Oxygen Molecule: A First-Principles Study

Absence of Ni on the outer surface of Sr doped La₂NiO₄single crystals

CO₂ sensing of La_0.875Ca_0.125FeO₃ in wet vapor: a comparison of experimental results and first-principles calculations

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Density functional theory study on oxygen adsorption in LaSrCoO4: An extended cathode material for solid oxide fuel cells

Cited by 23 publications

References 39 publications

Interaction of La2NiO4 (100) Surface with Oxygen Molecule: A First-Principles Study

Interaction of La2NiO4 (100) Surface with Oxygen Molecule: A First-Principles Study

Absence of Ni on the outer surface of Sr doped La2NiO4single crystals

CO2 sensing of La0.875Ca0.125FeO3 in wet vapor: a comparison of experimental results and first-principles calculations

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Interaction of La₂NiO₄ (100) Surface with Oxygen Molecule: A First-Principles Study

Interaction of La₂NiO₄ (100) Surface with Oxygen Molecule: A First-Principles Study

Absence of Ni on the outer surface of Sr doped La₂NiO₄single crystals

CO₂ sensing of La_0.875Ca_0.125FeO₃ in wet vapor: a comparison of experimental results and first-principles calculations