Novel catalytic properties of quadruple perovskites

Yamada, Ikuya

doi:10.1080/14686996.2017.1350557

Cited by 42 publications

(24 citation statements)

References 73 publications

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“…A quadruple perovskite has two distinct crystallographic sites for transition metal ions: pseudosquare A′ sites and octahedral B sites. In our recent study, CaCu 3 Fe 4 O 12 and AMn 7 O 12 (A = Ca or La) exhibited overpotentials that were lower than those of their corresponding simple perovskite oxides CaFeO 3 and AMnO 3 (A = Ca or La). − We proposed that the high catalytic activities of quadruple perovskite oxides are attributed to direct O–O bond formation via adjacent B sites on a (001) BO 2 -terminated surface or adjacent B and A′ sites on a (220) surface, in accordance with a comparison of bulk crystal structures. However, an in-depth study to elucidate the origin of high OER catalytic activity for quadruple perovskite oxides has not been performed.…”

Section: Introductionsupporting

confidence: 70%

Oxygen Evolution via the Bridging Inequivalent Dual-Site Reaction: First-Principles Study of a Quadruple-Perovskite Oxide Catalyst

et al. 2017

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Perovskite-type oxides composed of earth-abundant elements have been extensively studied as possible candidates for oxygen evolution reaction (OER) catalysts. In our recent study, quadruple perovskite oxides (e.g., Ca-Cu 3 Fe 4 O 12 and LaMn 7 O 12 ) displayed catalytic activity that was higher than that of simple perovskites (e.g., LaMnO 3 ), but the reason has not yet been unveiled. We have conducted firstprinciples calculations of the several surface energies of LaMn 7 O 12 and adsorption energies of OER intermediates on LaMn 7 O 12 using slab models to clarify the reaction mechanism. The Mn-rich surfaces, i.e., the (001) with BO 2 termination and (220) surfaces, are found to be more stable for LaMn 7 O 12 . It is found that all intermediates are preferentially adsorbed on the A′−B-bridge site on the LaMn 7 O 12 (220) surface, although only the B-top site was a stable adsorption site on the (001) surface of LaMn 7 O 12 and LaMnO 3 . The difference between theoretical overpotentials on the (220) surface of LaMn 7 O 12 and the (001) surface with BO 2 termination of LaMnO 3 is in good agreement with the experimental overpotential for OER. We propose a new design principle in which OER is enhanced via adsorption on the A′−B-bridge site consisting of two adjacent Mn sites {coordination-unsaturated pyramid [coordination number (CN) = 5] and coordination-saturated pseudosquare (CN = 4)}, where the adsorbates are strongly bound to the former and weakly bound to the latter.

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Section: Introductionsupporting

confidence: 70%

Oxygen Evolution via the Bridging Inequivalent Dual-Site Reaction: First-Principles Study of a Quadruple-Perovskite Oxide Catalyst

et al. 2017

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“…Recently, highly active and stable OER catalysis were reported for multiple-element transition metal oxides crystallizing in AA ′ 3 B 4 O 12 -type quadruple perovskite structure (Figure b). − In this structure, multiple transition metal ions occupy distinct crystallographic sites; Jahn–Teller active Cu 2+ and Mn 3+ ions occupy A ′-sites in pseudosquare coordination whereas typical 3d metal ions occupy B -sites in octahedral coordination. , Such an intelligible structure excludes substantial structural randomness and reasonably defines electronic states of constituent elements, enabling systematic investigations based on experimental and computational methods.…”

Section: Introductionmentioning

confidence: 97%

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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“…A quadruple perovskite oxide with the 1:3-type atomic ordering at A -site (see the crystal structure in Figure a), AA ′ 3 B 4 O 12 , has been attracting remarkable interest over ten years because of versatile electronic and functional properties originating from interplay of multiple transition-metal ions included in A ′- and B -sites. − Besides, a fractional carrier doping into transition metals can be achieved by simply replacing the element on the A -site by another, unlike partial substitutions of the A -site element as in the AB O 3 perovskite, which often suffers from a disorder, disrupting a precise evolution of the electronic states induced by doping. For instance, ferrimagnetic half-metallicity in LaCu 3 Mn 4 O 12 (La 3+ Cu 2+ 3 Mn 3.75+ 4 O 12 ) is achieved by electron doping into the ferrimagnetic insulator CaCu 3 Mn 4 O 12 (Ca 2+ Cu 2+ 3 Mn 4+ 4 O 12 ) by A -site substitution .…”

Section: Introductionmentioning

confidence: 99%

A Sequential Electron Doping for Quadruple Perovskite Oxides ACu₃Co₄O₁₂ (A = Ca, Y, Ce)

et al. 2020

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A novel quadruple perovskite oxide CeCu3Co4O12 has been synthesized in high-pressure and high-temperature conditions of 12 GPa and 1273 K. Rietveld refinement of the synchrotron X-ray powder diffraction pattern reveals that this oxide crystallizes in a cubic quadruple perovskite structure with the 1:3-type ordering of Ce and Cu ions at the A-site. X-ray absorption spectroscopy analysis demonstrates the valence-state transitions in the ACu3Co4O12 series (A = Ca, Y, Ce) from Ca2+Cu3+ 3Co3.25+ 4O12 to Y3+Cu3+ 3Co3+ 4O12 to Ce4+Cu2.67+ 3Co3+ 4O12, where the electrons are doped in the order from B-site (Co3.25+ → Co3+) to A′-site (Cu3+ → Cu2.67+). This electron-doping sequence is in stark contrast to the typical B-site electron doping for simple ABO3-type perovskite and quadruple perovskites CaCu3 B 4O12 (B = V, Cr, Mn), further differing from the monotonical A′-site electron doping for Na1–x La x Mn3Ti4O12 and A′- and B-site electron doping for AMn3V4O12 (A = Na, Ca, La). The differences in the electron-doping sequences are interpreted by rigid-band models, proposing a wide variety of electronic states for the complex transition-metal oxides containing the multiple valence-variable ions.

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Novel catalytic properties of quadruple perovskites

Cited by 42 publications

References 73 publications

Oxygen Evolution via the Bridging Inequivalent Dual-Site Reaction: First-Principles Study of a Quadruple-Perovskite Oxide Catalyst

Oxygen Evolution via the Bridging Inequivalent Dual-Site Reaction: First-Principles Study of a Quadruple-Perovskite Oxide Catalyst

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

A Sequential Electron Doping for Quadruple Perovskite Oxides ACu₃Co₄O₁₂ (A = Ca, Y, Ce)

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Novel catalytic properties of quadruple perovskites

Cited by 42 publications

References 73 publications

Oxygen Evolution via the Bridging Inequivalent Dual-Site Reaction: First-Principles Study of a Quadruple-Perovskite Oxide Catalyst

Oxygen Evolution via the Bridging Inequivalent Dual-Site Reaction: First-Principles Study of a Quadruple-Perovskite Oxide Catalyst

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

A Sequential Electron Doping for Quadruple Perovskite Oxides ACu3Co4O12 (A = Ca, Y, Ce)

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A Sequential Electron Doping for Quadruple Perovskite Oxides ACu₃Co₄O₁₂ (A = Ca, Y, Ce)