Magnetoresistance and Ferromagnetism in Disordered LaCu0.5Mn0.5O3 Perovskite

Cortés‐Gil, Raquel; Ruiz‐González, M. Luisa; Alonso, José María Rabal; Garcı́a-Hernández, M.; Hernando, A.; González‐Calbet, José M.

doi:10.1021/cm400655x

Cited by 15 publications

(10 citation statements)

References 55 publications

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“…CaCu 3 Ti 4 O 12 displayed much higher activity, thus the framework of quadruple perovskite structure is favorable for further enhancement of OER catalysis. Figure d compares OER activities between CaCu 3 Mn 4 O 12 and LaMn 0.5 Cu 0.5 O 3 , the latter of which consists of randomly mixed Mn 4+ and Cu 2+ ions at B -sites . The increased OER activity of LaMn 0.5 Cu 0.5 O 3 and much more enhanced activity of CaCu 3 Mn 4 O 12 are explained in line with synergistic effects and advantage of quadruple perovskite structure.…”

Section: Resultsmentioning

confidence: 93%

Synergistically Enhanced Oxygen Evolution Reaction Catalysis for Multielement Transition-Metal Oxides

Yamada

Takamatsu

Asai

et al. 2018

ACS Appl. Energy Mater.

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Transition metal oxides have been extensively investigated as novel catalysts for oxygen evolution reaction (OER). Partial elemental substitutions are effective ways to increase catalytic performance and such electronic interactions between multiple elements are known as synergistic effects. However, serious issues such as random atomic arrangement and ambiguous roles of constituent elements humper theoretical investigations for rational materials design. Herein, we describe systematic study on OER activity of AA′ 3 B 4 O 12 -type quadruple perovskite oxides, in which multiple transition metal ions are located at distinct crystallographic sites. Electrochemical measurements demonstrate that OER catalytic activities of quadruple perovskite oxide series, CaCu 3 B 4 O 12 (B = Ti, V, Cr, Mn, Fe, and Co), are all superior to those of simple perovskite counterparts CaBO 3 . The order of activity of B-site transition metal ions for CaBO 3 (Fe 4+ > Co 4+ ≫ Ti 4+ , V 4+ , Cr 4+ , Mn 4+ ) is retained in CaCu 3 B 4 O 12 , indicating that B-site ions play a primary role whereas A′-site Cu ions secondarily contribute to OER activity for CaCu 3 B 4 O 12 . Charge-transfer energies, energy differences between oxygen 2p band center and unoccupied 3d band center of B-site transition metal obtained from first-principles electronic-state calculations, illustrate that OER overpotentials of quadruple perovskite oxides are lower than simple perovskite oxides by ∼150 mV. These findings propose a simple avenue to realize enhanced OER activity for multiple transition-metal ions.

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Section: Resultsmentioning

confidence: 93%

Synergistically Enhanced Oxygen Evolution Reaction Catalysis for Multielement Transition-Metal Oxides

Yamada

Takamatsu

Asai

et al. 2018

ACS Appl. Energy Mater.

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“…Creating the Mn vacancies in PrMn 0.9 O 3 however decreases the Mn 4+ fraction, reducing its moment. The AFM ordering is driven by the short-range disordered Mn 3+ –O–Mn 3+ and Mn 4+ –O–Mn 4+ superexchange interactions, which is prominent with higher Mn vacancies . The region below ∼50 K can be ascribed to the glassy behavior of the spins .…”

Section: Resultsmentioning

confidence: 99%

“…The AFM ordering is driven by the short-range disordered Mn 3+ −O−Mn 3+ and Mn 4+ −O− Mn 4+ superexchange interactions, which is prominent with higher Mn vacancies. 27 The region below ∼50 K can be ascribed to the glassy behavior of the spins. 6 The high anisotropy of the frozen spin-glass-like region was suggested by the existing bifurcation of the ZFC and FC curves even at a high applied field of 1 T (Figure S5).…”

Section: Inorganic Chemistrymentioning

confidence: 99%

Extensive Parallelism between Crystal Parameters and Magnetic Phase Transitions of Unusually Ferromagnetic Praseodymium Manganite Nanoparticles

et al. 2016

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The alterations in physical property across different space groups of the same material are sometimes conveniently reflected by the crystal structure as a function of temperature. However, mirroring the physical property and crystal parameters over a wide range of temperatures within the same space group is quite unusual. Remarkably, Rietveld analyses of the X-ray diffraction patterns of PrMn 0.9 O 3 (ABO 3 ) nanoparticles (NPs) with a constant Pnma space group from 300 to 10 K could successfully predict the four magnetic phases, viz. paramagnetic, antiferromagnetic (AFM), ferromagnetic (FM), and spin-glass-like ordering. The increase in Mn−O−Mn bond angles and tolerance factor leads to FM ordering below ∼100 K in usually AFM PrMn 0.9 O 3 NPs. The concurrent decrease of lattice cell volume and Mn−O−Mn bond angles near the AFM to FM transition temperature (T c ) suggests that the AFM character increases just above T c due to atomic deformations and reduced Mn−Mn separation. The predictions from crystal structure refinement were successfully verified from the cooling path of the temperature-dependent field-cooled magnetization measurements. A mechanism involving incoherent spin reversal due to competition between the neighboring spins undergoing antiparallel to parallel spin rotations was suggested. The structure− property parallelism was cross-checked with the A-site vacant Pr 0.9 MnO 3.2 NPs.

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“…The analysis of the diffractograms was carried out with the software WinXPOW using reference data from the ICDD and ICSD databases. References from ICDD are given below including the chemical formula and the card number: Cu, 00-004-0836; La 2 O 3 , 00-005-0602; and La 2 CuO 4 , 00-030-0487; References from ICSD are given below including the chemical formula and the database code: LaCu 0.5 Mn 0.5 O 3 , 193762; LaCu 0.3 Mn 0.7 O 3 , 92191 …”

Section: Methodsmentioning

confidence: 99%

Who Does the Job? How Copper Can Replace Noble Metals in Sustainable Catalysis by the Formation of Copper–Mixed Oxide Interfaces

et al. 2022

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Following the need for an innovative catalyst and material design in catalysis, we provide a comparative approach using pure and Pd-doped LaCu x Mn 1– x O 3 ( x = 0.3 and 0.5) perovskite catalysts to elucidate the beneficial role of the Cu/perovskite and the promoting effect of Cu y Pd x /perovskite interfaces developing in situ under model NO + CO reaction conditions. The observed bifunctional synergism in terms of activity and N 2 selectivity is essentially attributed to an oxygen-deficient perovskite interface, which provides efficient NO activation sites in contact with in situ exsolved surface-bound monometallic Cu and bimetallic CuPd nanoparticles. The latter promotes the decomposition of the intermediate N 2 O at low temperatures, enhancing the selectivity toward N 2 . We show that the intelligent Cu/perovskite interfacial design is the prerequisite to effectively replace noble metals by catalytically equally potent metal–mixed-oxide interfaces. We have provided the proof of principle for the NO + CO test reaction but anticipate the extension to a universal concept applicable to similar materials and reactions.

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Magnetoresistance and Ferromagnetism in Disordered LaCu_0.5Mn_0.5O₃ Perovskite

Cited by 15 publications

References 55 publications

Synergistically Enhanced Oxygen Evolution Reaction Catalysis for Multielement Transition-Metal Oxides

Synergistically Enhanced Oxygen Evolution Reaction Catalysis for Multielement Transition-Metal Oxides

Extensive Parallelism between Crystal Parameters and Magnetic Phase Transitions of Unusually Ferromagnetic Praseodymium Manganite Nanoparticles

Who Does the Job? How Copper Can Replace Noble Metals in Sustainable Catalysis by the Formation of Copper–Mixed Oxide Interfaces

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