Crystal Chemistry of Cobalt Oxides

Raveau, B.; Seikh, Md. Motin

doi:10.1002/9783527645527.ch1

Cobalt Oxides 2012

DOI: 10.1002/9783527645527.ch1

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Crystal Chemistry of Cobalt Oxides

B. Raveau

Md. Motin Seikh

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Cited by 6 publications

References 340 publications

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Structural, Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO_2.67

Waidha

Siddiqui

Ikeda

et al. 2021

Chemistry A European J

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A new vacancy ordered, anion deficient perovskite modification with composition of BaCoO2.67 (Ba3Co3O8□1) has been prepared via a two‐step heating process. Combined Rietveld analysis of neutron and X‐ray powder diffraction data shows a novel ordering of oxygen vacancies not known before for barium cobaltates. A combination of neutron powder diffraction, magnetic measurements, and density functional theory (DFT) studies confirms G‐type antiferromagnetic ordering. From impedance measurements, the electronic conductivity of the order of 10−4 S cm−1 is determined. Remarkably, the bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is found to be comparable to that of Ba0.5Sr0.5Co0.8Fe0.2O3–y, confirming that charge‐ordered anion deficient non‐cubic perovskites can be highly efficient catalysts.

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Structural, Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO_2.67

Waidha

Siddiqui

Ikeda

et al. 2021

Chemistry A European J

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Strong Co–Mo Interaction behind Unexpected Physicochemical Properties in SrMo_0.9Co_0.1O_3−δ Perovskite

et al. 2021

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A novel combined chemical procedure was employed to synthesize a homogeneous SrMo0.9Co0.1O3−δ (SMC) perovskite at lower temperatures (900 °C). The physicochemical properties of SMC were analyzed by means of in situ X-ray diffraction and X-ray absorption spectroscopy experiments under reducing and oxidizing conditions from 20 to 700 °C. The study revealed a strong interaction between Mo and Co cations in the SMC perovskite, which led to their unexpected oxidation number speciation and a critical modification of their first coordination shell. Perovskite-like unit cells containing Co in their center can drastically increase the occupation number of oxygen anions, enhancing SMC oxygen storage capability. Under reducing conditions, these loosely bonded anions were easily released from the material to chemically react with H2 in the gas phase. These findings bring novel insights into the physicochemical processes that take place in SMC materials and give rise to the catalytic and electrochemical activity that makes this material a candidate for intermediate temperature-SOFC anode application.

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Catalytic Dynamics and Oxygen Diffusion in Doped PrBaCo₂O_5.5+δ Thin Films

Enriquez

Bao

et al. 2015

ACS Appl. Mater. Interfaces

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The Sr and Fe codoped double perovskites PrBaCo2O5.5+δ (PrBCO) thin films of Pr(Ba0.5Sr0.5)(Co1.5Fe0.5)O5.5+δ (PBSCFO) were epitaxially grown for chemical catalytic studies. The resistance behavior of PBSCFO epitaxial films was monitored under the switching flow of reducing and oxidizing gases as a function of the gas flow time, t, using an electrical conductivity relaxation (ECR) experimental setup. The R(t) vs t relationships determined at various temperatures show the occurrence of two oxidation processes, Co(2+)/Co(3+) ↔ Co(3+) and Co(3+) ↔ Co(3+)/Co(4+). Mathematical fitting of the observed R(t) vs t relationships was carried out using Fick's second law for one-dimensional diffusion of charge carriers to derive the diffusivity D(T) and τ(T) for the two processes at various temperatures, T. The D(T) vs T relationships were analyzed in terms of the Arrhenius relationship to find the activation energies Ea for each process. Oscillations in the dR(t)/dt plots, observed under oxidation reactions, were discussed in terms of a layer-by-layer oxygen vacancy exchange diffusion mechanism. Our work suggests that thin films of LnBCO (Ln = lanthanide) with their A and B sites doped as in PBSCFO are excellent candidates for the development of low or intermediate temperature energy conversion devices and gas sensor applications.

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Crystal Chemistry of Cobalt Oxides

Cited by 6 publications

References 340 publications

Structural, Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO_2.67

Structural, Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO_2.67

Strong Co–Mo Interaction behind Unexpected Physicochemical Properties in SrMo_0.9Co_0.1O_3−δ Perovskite

Catalytic Dynamics and Oxygen Diffusion in Doped PrBaCo₂O_5.5+δ Thin Films

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Crystal Chemistry of Cobalt Oxides

Cited by 6 publications

References 340 publications

Structural, Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO2.67

Structural, Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO2.67

Strong Co–Mo Interaction behind Unexpected Physicochemical Properties in SrMo0.9Co0.1O3−δ Perovskite

Catalytic Dynamics and Oxygen Diffusion in Doped PrBaCo2O5.5+δ Thin Films

Contact Info

Product

Resources

About

Structural, Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO_2.67

Structural, Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO_2.67

Strong Co–Mo Interaction behind Unexpected Physicochemical Properties in SrMo_0.9Co_0.1O_3−δ Perovskite

Catalytic Dynamics and Oxygen Diffusion in Doped PrBaCo₂O_5.5+δ Thin Films