Ordering Of Oxygen Vacancies Research Articles

Oxygen vacancy order–disorder transition process during topotactic filament formation in a perovskite oxide tracked by Raman microscopy and transmission electron microscopy

Vacancy-ordered perovskite oxides are attracting attention due to their diverse functions such as resistive switching, electrocatalytic activity, oxygen diffusivity, and ferroelectricity. It is important to clarify the chemical lattice strains arising from compositional changes and the associated vacancy order–disorder phase transitions at the atomic scale. Here, we elucidate the intermediate process of a topotactic phase transition in Ca-doped bismuth ferrite films consisting of alternating stacks of oxygen perovskite layers and a brownmillerite-type oxygen vacancy layer. We use Raman spectroscopy and transmission electron microscopy to closely examine the evolution of local strains exerted on the constituent sub-layers by electrochemical oxidation. A negative Raman chemical shift is observed during oxidation, which is linearly correlated with the local negative chemical expansivity of the oxygen layer. It seemingly contradicts with the general trend that oxides undergo lattice contraction upon oxidation. Oxygen vacancies initially confined in the vacancy layers can be understood to diffuse into the oxygen layers during melting of the ordered structure. The finding deepens our understanding of the electro-chemo-mechanical coupling of vacancy-ordered oxides.

Informatics-Based Learning of Oxygen Vacancy Ordering Principles in Oxygen-Deficient Perovskites.

Ordered oxygen vacancies (OOVs) in perovskites can exhibit long-range order and may be used to direct materials properties through modifications in electronic structures and broken symmetries. Based on the various vacancy patterns observed in previously known compounds, we explore the ordering principles of oxygen-deficient perovskite oxides with ABO2.5 stoichiometry to identify other OOV variants. We performed first-principles calculations to assess the OOV stability on a data set of 50 OOV structures generated from our bespoke algorithm. The algorithm employs uniform planar vacancy patterns on (111) pseudocubic perovskite layers and the approach proves effective for generating stable OOV patterns with minimal computational loads. We find as expected that the major factors determining the stability of OOV structures include coordination preferences of transition metals and elastic penalties resulting from the assemblies of polyhedra. Cooperative rotational modes of polyhedra within the OOV structures reduce elastic instabilities by optimizing the bond valence of A- and B cations. This finding explains the observed formation of vacancy channels along low-index crystallographic directions in prototypical OOV phases. The identified ordering principles enable us to devise other stable vacancy patterns with longer periodicity for targeted property design in yet to be synthesized compounds.

Ordering of oxygen vacancies in hydroxyapatite under electron irradiation

Understanding the mechanisms of radiation induced defect generation is essential for assessment of materials to be used in nuclear environments. In the current work, we investigate the effect of 10 MeV electron irradiation on the generation and possible ordering of defects/oxygen vacancies in hydroxyapatite (HAP) powders. Comprehensive analyses of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Electron Paramagnetic Resonance (EPR) and Raman spectra establish that (a) HAP has a high level of structural stability even after exposure to electron irradiation; (b) irradiation leads to the generation of surface defects/oxygen vacancy predominantly in the PO43− polyanion site, particularly in part of asymmetric bonding within the P–O bonds and (c) there is noticeable evidence for an ordered arrangement of oxygen vacancies within the HAP irradiated at 1 MGy dose. These radiation-induced defects, such as oxygen vacancies, can migrate within the HAP lattice, leading to formation of defect/oxygen vacancies clusters which ultimately results in the ordering tendency of oxygen vacancies within the lattice. The observed ordering, as evidenced by the photoluminescence intensities, aligns with the sequence HAP-1MGy > HAP-20MGy > HAP, providing further support for the presence of ordered oxygen vacancies.

Structural Characterization of La0.6Sr0.4CoO3-δ Thin Films Grown on (100)-, (110)-, and (111)-Oriented La0.95Sr0.05Ga0.95Mg0.05O3-δ.

In this study, a detailed structural characterization of epitaxial La0.6Sr0.4CoO3-δ (LSC) films grown in (100), (110), and (111) orientations was conducted. LSC is a model air electrode material in solid oxide fuel and electrolysis cells and understanding the correlation of bulk structure and catalytic activity is essential for the design of future electrode materials. Thin films were grown on single crystals of the perovskite material La0.95Sr0.05Ga0.95Mg0.05O3-δ cut in three different directions. This enabled an examination of structural details at the atomic scale for a realistic material combination in solid oxide cells. The investigation involved the application of atomic force microscopy, X-ray diffraction, and high-resolution transmission electron microscopy to explore the distinct properties of these thin films. Interestingly, ordering phenomena in both cationic as well as anionic sublattices were found, despite the fact that the thin films were never at higher temperatures than 600 °C. Cationic ordering was found in spherical precipitates, whereas the ordering of oxygen vacancies led to the partial transition to brownmillerite in all three orientations. Our results indicate a very high oxygen vacancy concentration in all three thin films. Lattice strains in-plane and out-of-plane was measured, and its implications for the structural modifications are discussed.

Tailored (La0.2Pr0.2Nd0.2Tb0.2Dy0.2)2Ce2O7 as a Highly Active and Stable Nanocatalyst for the Oxygen Evolution Reaction.

Designing highly active and robust catalysts for the oxygen evolution reaction is key to improving the overall efficiency of the water splitting reaction. It has been previously demonstrated that evaporation induced self-assembly (EISA) can be used to synthesize highly porous and high surface area cerate-based fluorite nanocatalysts, and that substitution of Ce with 50% rare earth (RE) cations significantly improves electrocatalyst activity. Herein, the defect structure of the best performing nanocatalyst in the series are further explored, Nd2Ce2O7, with a combination of neutron diffraction and neutron pair distribution function analysis. It is found that Nd3 + cation substitution for Ce in the CeO2 fluorite lattice introduces higher levels of oxygen Frenkel defects and induces a partially reduced RE1.5Ce1.5O5 + x phase with oxygen vacancy ordering. Significantly, it is demonstrated that the concentration of oxygen Frenkel defects and improved electrocatalytic activity can be further enhanced by increasing the compositional complexity (number of RE cations involved) in the substitution. The resulting novel compositionally-complex fluorite- (La0.2Pr0.2Nd0.2Tb0.2Dy0.2)2Ce2O7 is shown to display a low OER overpotential of 210 mV at a current density of 10 mAcm-2 in 1M KOH, and excellent cycling stability. It is suggested that increasing the compositional complexity of fluorite nanocatalysts expands the ability to tailor catalystdesign.

Hydrogen-Driven Low-Temperature Topotactic Transition in Nanocomb Cobaltite for Ultralow Power Ionic-Magnetic Coupled Applications.

We reversibly control ferromagnetic-antiferromagnetic ordering in an insulating ground state by annealing tensile-strained LaCoO3 films in hydrogen. This ionic-magnetic coupling occurs due to the hydrogen-driven topotactic transition between perovskite LaCoO3 and brownmillerite La2Co2O5 at a lower temperature (125-200 °C) and within a shorter time (3-10 min) than the oxygen-driven effect (500 °C, tens of hours). The X-ray and optical spectroscopic analyses reveal that the transition results from hydrogen-driven filling of correlated electrons in the Co 3d-orbitals, which successively releases oxygen by destabilizing the CoO6 octahedra into CoO4 tetrahedra. The transition is accelerated by surface exchange, diffusion of hydrogen in and oxygen out through atomically ordered oxygen vacancy "nanocomb" stripes in the tensile-strained LaCoO3 films. Our ionic-magnetic coupling with fast operation, good reproducibility, and long-term stability is a proof-of-principle demonstration of high-performance ultralow power magnetic switching devices for sensors, energy, and artificial intelligence applications, which are keys for attaining carbon neutrality.

Enhanced chemical looping CO2 conversion activity and thermal stability of perovskite LaCo1-xAlxO3 by Al substitution.

The reverse water-gas shift chemical looping (RWGS-CL) process that utilizes redox reactions of metal oxides is promising for converting CO2 to CO at low temperatures. Metal oxides with perovskite structures, particularly, perovskite LaCoO3 are promising frameworks for designing RWGS-CL materials as they can often release oxygen atoms topotactically to form oxygen vacancies. In this study, solid solutions of perovskite LaCo1-xAlxO3 (0 ≤ x ≤ 1), which exhibited high CO production capability and thermal stability under the RWGS-CL process, were developed. Al-substituted LaCo0.5Al0.5O3 (x = 0.5) exhibited a 4.1 times higher CO production rate (2.97 × 10-4 CO mol g-1 min-1) than that of LaCoO3 (x = 0; 0.73 × 10-4 CO mol g-1 min-1). Diffuse reflectance infrared Fourier transform spectroscopy studies suggested that an increase in CO2 adsorption sites produced by the coexistence of Al and Co was responsible for the enhancement of CO production rate. Furthermore, LaCo0.5Al0.5O3 maintained its perovskite structure during the RWGS-CL process at 500 °C without significant decomposition, whereas LaCoO3 decomposed into La2O3 and Co0. In situ X-ray diffraction study revealed that the high thermal stability was attributed to the suppression of phase transition into a brownmillerite structure with ordered oxygen vacancies. These findings provide a critical design approach for the industrial application of perovskite oxides in the RWGS-CL processes.

Tunable ferroelectricity in oxygen-deficient perovskites with Grenier structure

Using first-principles calculations, we predict that tunable ferroelectricity can be realized in oxide perovskites with the Grenier structure and ordered oxygen vacancies. Specifically, we show that R1/3A2/3FeO2.67 solids (where R is a rare-earth ion and A an alkaline-earth cation) exhibit polar phases, with a spontaneous polarization tunable by an appropriate choice of R and A. We find that larger cations combined with small R elements lead to a maximum in the polarization and to a minimum in the energy barriers required to switch the sign of the polarization. Ferroelectricity arises from cooperative distortions of octahedral and tetrahedral units, where a combination of rotational and sliding modes controls the emergence of polarization within three-dimensional connected layers. Our results indicate that polar Grenier phases of oxide perovskites are promising materials for microelectronic applications and, in general, for the study of phenomena emerging from breaking inversion symmetry in solids.

Electrocatalytic Properties of Oxygen-Deficient Perovskites Ca3Fe3-xMnxO8 (x = 1-2) for the Hydrogen Evolution Reaction.

We have demonstrated a systematic trend in the electrocatalytic activity for the hydrogen evolution reaction (HER) and its correlations with transition-metal type, structural order, and electrical conductivity. The materials studied in this work, Ca3FeMn2O8 (CaFe1/3Mn2/3O3-1/3), Ca3Fe1.5Mn1.5O8, and Ca3Fe2MnO8, belong to the family of oxygen-deficient perovskites and show a gradual increase in the ordering of oxygen vacancies. Ca3FeMn2O8 (CaFe1/3Mn2/3O3-1/3) contains randomly distributed oxygen vacancies, which begin to order in Ca3Fe1.5Mn1.5O8, and are fully ordered in Ca3Fe2MnO8. The gradual increase in the structural order is associated with a systematic enhancement of the electrocatalytic activity for HER in acidic conditions, Ca3FeMn2O8 < Ca3Fe1.5Mn1.5O8 < Ca3Fe2MnO8. While the improvement of the HER activity is also associated with an increase in the Fe content, we have shown that the type of structural order plays a more important role. We demonstrated this effect by control experiments on an analogous material where all Mn was substituted by Fe, leading to a different type of structural order and showing an inferior HER activity compared to the above three materials. Furthermore, electrical conductivity studies in a wide range of temperatures, 25-800 °C, indicate that the trend in the electrical conductivity is the same as that of the HER activity. These findings reveal several important structure-property relationships and highlight the importance of synergistic effects in enhancing the electrocatalytic properties.

Oxygen Vacancy Ordering and Molten Salt Corrosion Behavior of ZnO-Doped CeYSZ for Solid Oxide Membranes.

Although 4Ce4YSZ has high corrosion resistance, it faces challenges concerning its sinterability and ionic conductivity. Therefore, we studied destabilization behavior caused by corrosion and oxygen vacancy ordering according to ZnO doping. Powders of (4Ce4YSZ)1-x(ZnO)x (x = 0.5, 1, 2, 4 mol%) were synthesized using the sol-gel method. With the addition of ZnO, the cubic phase increased, and secondary phases were not observed. The (111) peak showed a higher angle shift in ZnO-doped 4Ce4YSZ compared to 4Ce4YSZ, and TEM-SAED revealed a reduction in the spacing of the (011)t plane, suggesting lattice contraction due to the substitution of the smaller Zn2+ (60 Å) for Zr4+ (84 Å) in the lattice. The local atomic structure analysis was conducted using EXAFS to investigate the oxygen vacancy ordering behavior. Zr K-edge Fourier transform data revealed a decrease in the Zr-O1 peak intensity with an increasing amount of ZnO doping, indicating an increase in oxygen vacancies. The Zr-O1 peak position shifted to the right, leading to an increase in the Zr-O1 interatomic distance. In the Y K-edge Fourier transform data, the Y-O1 peak intensity did not decrease, and there was little variation in the Y-O1 interatomic distance. These results suggest that the oxygen vacancies formed due to ZnO doping are located in the neighboring oxygen shell of Zn, rather than in the neighboring oxygen shells of Y and Zr. Impedance measurements were conducted to measure the conductivity, and as the amount of ZnO doping increased, the total conductivity increased, while the activation energy decreased. The increase in oxygen vacancies by ZnO doping contributed to the enhancement of conductivity, and it is considered that these created oxygen vacancies did not interact with Zn2+ and did not form defect associations. Fluoride-based molten salts were introduced to the specimens to assess the corrosion behavior in a molten salt environment. Yttrium depletion layers (YDLs) were formed on the surfaces of all specimens due to the leaching of yttrium. However, Ce remained relatively stable at the interface according to EDS line scans, suggesting a reduction in the phase transformation (cubic, tetragonal to monoclinic) typically associated with yttrium leaching in YSZ.

Selective CO2 photoreduction to C2 hydrocarbon via synergy between metastable ordered oxygen vacancies and hydrogen spillover over TiO2 nanobelts

The development of photocatalysts with desirable compositions and structures to improve the selectivity of CO2 conversion to hydrocarbon remains a challenging goal. In this study, we present a strategy of defected TiO2 nanobelts with metastable ordered oxygen vacancies by a simple Pd-catalyzed oxygen reduction method under anoxic condition. Ordered oxygen vacancies not only provide the driving force and channel for the directional movement of photoinduced electrons by modulating built-in electric field, but also promote CO2 adsorption and activation. Pd nanoparticles (Pd NPs) boosted dissociation of H2O to increase H* coverage and promoted the protonation of the intermediates via hydrogen spillover. The synergistic effect of ordered oxygen vacancies and hydrogen spillover contributed to the enhanced photocatalytic reduction of CO2 toward C2 products. The maximum selectivity of C2 products can reach 51.45% with an evolution rate of 25.987 μmol·g−1·h−1. This strategy provides a convenient method for designing a selective CO2 conversion photocatalyst.

Tailoring Ion Ordering in Perovskite Oxide for High-Temperature Oxygen Evolution Reaction.

Perovskites exhibit excellent high-temperature oxygen evolution reaction (OER) activities as the anodes of solid oxide electrolysis cells (SOECs). However, the relationship between ion ordering and OER performances is rarely investigated. Herein, a series of PrBaCo2-x Fex O5+δ perovskites with tailored ion orderings are constructed. Physicochemical characterizations and density functional theory calculations confirm that the oxygen bulk migration and surface transport capacities as well as the OER activities are promoted by the A-site cation ordering, but weakened by the oxygen vacancy ordering. Hence, SOEC with the A-site-ordered and oxygen-vacancy-disordered PrBaCo2 O5+δ anode exhibits the highest performance of 3.40 A cm-2 at 800 °C and 2.0 V. This work sheds light on the critical role of ion orderings in the high-temperature OER performance and paves a new way for screening novel anode materials of SOECs.

Tailoring Ion Ordering in Perovskite Oxide for High‐Temperature Oxygen Evolution Reaction

AbstractPerovskites exhibit excellent high‐temperature oxygen evolution reaction (OER) activities as the anodes of solid oxide electrolysis cells (SOECs). However, the relationship between ion ordering and OER performances is rarely investigated. Herein, a series of PrBaCo2−xFexO5+δ perovskites with tailored ion orderings are constructed. Physicochemical characterizations and density functional theory calculations confirm that the oxygen bulk migration and surface transport capacities as well as the OER activities are promoted by the A‐site cation ordering, but weakened by the oxygen vacancy ordering. Hence, SOEC with the A‐site‐ordered and oxygen‐vacancy‐disordered PrBaCo2O5+δ anode exhibits the highest performance of 3.40 A cm−2 at 800 °C and 2.0 V. This work sheds light on the critical role of ion orderings in the high‐temperature OER performance and paves a new way for screening novel anode materials of SOECs.

Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO3 thin films

Transition metal oxides are promising candidates for the next generation of spintronic devices due to their fascinating properties that can be effectively engineered by strain, defects, and microstructure. An excellent example can be found in ferroelastic LaCoO3 with paramagnetism in bulk. In contrast, unexpected ferromagnetism is observed in tensile-strained LaCoO3 films, however, its origin remains controversial. Here we simultaneously reveal the formation of ordered oxygen vacancies and previously unreported long-range suppression of CoO6 octahedral rotations throughout LaCoO3 films. Supported by density functional theory calculations, we find that the strong modification of Co 3d-O 2p hybridization associated with the increase of both Co-O-Co bond angle and Co-O bond length weakens the crystal-field splitting and facilitates an ordered high-spin state of Co ions, inducing an emergent ferromagnetic-insulating state. Our work provides unique insights into underlying mechanisms driving the ferromagnetic-insulating state in tensile-strained ferroelastic LaCoO3 films while suggesting potential applications toward low-power spintronic devices.

Topotactically induced oxygen vacancy order in nickelate single crystals

The strong structure-property coupling in rare-earth nickelates has spurred the realization of new quantum phases in rapid succession. Recently, topotactic transformations have provided a new platform for the controlled creation of oxygen vacancies and, therewith, for the exploitation of such coupling in nickelates. Here, we report the emergence of oxygen vacancy ordering in Pr$_{0.92}$Ca$_{0.08}$NiO$_{2.75}$ single crystals obtained via a topotactic reduction of the perovskite phase Pr$_{0.92}$Ca$_{0.08}$NiO$_{3}$, using CaH$_2$ as the reducing agent. We unveil a brownmillerite-like ordering pattern of the vacancies by high-resolution scanning transmission electron microscopy, with Ni ions in alternating square-pyramidal and octahedral coordination along the pseudocubic [100] direction. Furthermore, we find that the crystal structure acquires a high level of internal strain, where wavelike modulations of polyhedral tilts and rotations accommodate the large distortions around the vacancy sites. Our results suggest that atomic-resolution electron microscopy is a powerful method to locally resolve unconventional crystal structures that result from the topotactic transformation of complex oxide materials.

Coordination Tailoring of Epitaxial Perovskite-Derived Iron Oxide Films for Efficient Water Oxidation Electrocatalysis

Cost-effective perovskite oxides have recently offered intriguing promise for electrochemical energy storage and conversion systems. Despite the breadth of previously studied electronic structures and properties, the sluggish kinetics of the oxygen evolution reaction (OER) of perovskite oxides basically restrict their applications in metal–air batteries and electrolytic cells. In this work, we report on a highly efficient OER activity of perovskite-derived SrFeO3−δ (0.0 ≤ δ ≤ 1.0) single-crystal films by selectively tuning the Fe–O coordination structure and film orientation. Our findings show that the facile anionic oxygen-induced topotactic brownmillerite phase of the SrFeO2.5 film possesses superior electrocatalytic performance with a small overpotential and Tafel slope, which is mainly attributed to the peculiar Fe–O coordination framework along with ordered oxygen vacancy channels. Moreover, the low adsorption free energy and small charge transfer resistance could further boost the electrocatalytic OER performance of the (111)-oriented BM-SrFeO2.5 films. This delicate tailoring of the epitaxial SrFeO3−δ films enables the tunable catalytic reaction pathways and concomitantly efficient OER kinetics, which has significant implications for the rational design of cost-effective and high-performance perovskite-based electrocatalysts.

Evidence of vacancy ordered structures in PuO2-x and AmO2-x from first-principles calculations.

A combination of first-principles calculations and cluster expansion method is used to study ordering of oxygen vacancies in PuO2-x and AmO2-x. Vacancy ordered stable/metastable structures of composition Pu8O15 (PuO1.875), Pu6O11 (PuO1.833), Pu8O14 (PuO1.75) and Am10O19 (AmO1.90), Am8O15 (AmO1.875), Am10O18 (AmO1.80), Am8O13 (AmO1.625) are identified in PuO2-x and AmO2-x, respectively, from cluster expansion calculations. A comparison of formation enthalpies of vacancy ordered and vacancy disordered structures shows that Am8O15 (AmO1.875) and Am8O13 (AmO1.625) are more stable by 52 and 55 meV per atom, respectively, compared to their disordered counterparts. Similarly, vacancy ordered Pu8O15 (PuO1.875) and Pu8O14 (PuO1.75) structures are more stable compared to the disordered structures by 10 and 8 meV per atom, respectively. In contrast, the disordered PuO1.625 structure is more stable compared to the cluster expansion generated structures. The vacancy ordered structures are mechanically stable and their bulk modulus, Young's modulus, shear modulus and Poisson's ratio are reported.

Topotactic redox cycling in SrFeO2.5+δ explored by 3D electron diffraction in different gas atmospheres

Using in situ 3D electron diffraction on SrFeOx nanocrystals during the solid–gas redox reaction, we uncovered oxygen-vacancy ordering and domain formation not observable by in situ solid–gas bulk diffraction techniques.

Realizing Metastable Cobaltite Perovskite via Proton-Induced Filling of Oxygen Vacancy Channels.

The interaction between transition-metal oxides (TMOs) and protons has become a key issue in magneto-ionics and proton-conducting fuel cells. Until now, most investigations on oxide-proton reactions rely on electrochemical tools, while the direct interplay between protons and oxides remains basically at simple dissolution of metal oxides by an acidic solution. In this work, we find classical TMO brownmillerite SrCoO2.5 (B-SCO) films with ordered oxygen vacancy channels experiencing an interesting transition to a metastable perovskite phase (M-SCO) in a weak acidic solution. M-SCO exhibits a strong ferromagnetism (1.01 μB/Co, Tc > 200 K) and a greatly elevated electrical conductivity (∼104 of pristine SrCoO2.5), which is similar to the prototypical perovskite SrCoO3. Besides, such M-SCO tends to transform back to B-SCO in a vacuum environment or heating at a relatively low temperature. Two possible mechanisms (H2O addition/active oxygen filling) have been proposed to explain the phenomenon, and the control experiments demonstrate that the latter mechanism is the dominant process. Our work finds a new way to realize cobaltite perovskite with enhanced magnetoelectric properties and may deepen the understanding of oxide-proton interaction in an aqueous solution.

Defect equilibrium and charge transport in R0.25Sr0.75FeO3−δ (R = La, Nd, Y, Ho): The effect of cation type

The perovskite-type oxides of R0.25Sr0.75FeO3−δ series for R = La, Nd, Y, Ho were subjected to X-ray and electron diffraction studies, thermogravimetric and dilatometric measurements. Coulometric titration and four-probe DC techniques were used to obtain data on oxygen content and electrical conductivity of the oxides in the range of oxygen partial pressure from 10−19 to 0.5 atm at 750–950 °C. A decrease in the size of R-cation in R0.25Sr0.75FeO3−δ was found to result in a decrease in the oxygen content in the oxides, thermal expansion, and electrical conductivity. In case of Y and Ho, an extra factor, in addition to the cation radius, affecting the oxide properties, is argued to be the limited oxygen coordination, which promotes local ordering in the respective oxides. This statement was confirmed by electron diffraction study, which detected incommensurate diffuse scattering as the evidence of partial local ordering of cations in the A sublattice in combination with the ordering of oxygen vacancies. This partial local ordering affects strongly functional properties of Y and Ho containing oxides. In particular, oxygen-ion conductivity at 950 °C decreases from 0.328 ± 0.005 to 0.055 ± 0.003 S/cm in response to the substitution of La in R0.25Sr0.75FeO3−δ by Y.