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At least 55 records · Page 3

Low-energy spin dynamics in rare-earth perovskite oxides

We review recent studies of spin dynamics in rare-earth orthorhombic perovskite oxides of the type RMO 3 , where R is a rare-earth ion and M is a transition-metal ion, using single-crystal inelastic neutron scattering (INS). After a short introduction to the magnetic INS technique in general, the results of INS experiments on both transition-metal and rare-earth subsystems for four selected compounds (YbFeO 3 , TmFeO 3 , YFeO 3 , YbAlO 3 ) are presented. We show that the spectrum of magnetic excitations consists of two types of collective modes that are well separated in energy: gapped magnons with a typical bandwidth of <70 meV, associated with the antiferromagnetically (AFM) ordered transition-metal subsystem, and AFM fluctuations of <5 meV within the rare-earth subsystem, with no hybridization of those modes. We discuss the high-energy conventional magnon excitations of the 3d subsystem only briefly, and focus in more detail on the spectacular dynamics of the rare-earth sublattice in these materials. We observe that the nature of the ground state and the low-energy excitation strongly depends on the identity of the rare-earth ion. In the case of non-Kramers ions, the low-symmetry crystal field completely eliminates the degeneracy of the multiplet state, creating a rich magnetic field-temperature phase diagram. In the case of Kramers ions, the resulting ground state is at least a doublet, which can be viewed as an effective quantum spin-1/2. Equally important is the fact that in Yb-based materials the nearest-neighbor exchange interaction dominates in one direction, despite the three-dimensional nature of the orthoperovskite crystal structure. The observation of a fractional spinon continuum and quantum criticality in YbAlO3 demonstrates that Kramers rare-earth based magnets can provide realizations of various aspects of quantum low-dimensional physics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Compositionally complex perovskite oxides: Discovering a new class of solid electrolytes with interface-enabled conductivity improvements

Compositionally complex ceramics (CCCs), including high-entropy ceramics, offer a vast, unexplored compositional space for materials discovery. Herein, we propose and demonstrate strategies for tailoring CCCs via a combination of non-equimolar compositional designs and control of grain boundaries (GBs) and microstructures. Using oxide solid electrolytes for all-solid-state batteries as an example, we have discovered a class of compositionally complex perovskite oxides (CCPOs) with improved lithium ionic conductivities beyond the limit of conventional doping. For example, we demonstrate that the ionic conductivity can be improved by >60% in (Li 0.375 Sr 0.4375 )(Ta 0.375 Nb 0.375 Zr 0.125 Hf 0.125 )O 3-δ compared with the (Li 0.375 Sr 0.4375 )(Ta 0.75 Zr 0.25 )O 3-δ (LSTZ) baseline. Furthermore, the ionic conductivity can be improved by another >70% via quenching, achieving >270% of the LSTZ. Notably, we demonstrate GB-enabled conductivity improvements via both promoting grain growth and altering GB structures through compositional designs and processing. In a broader perspective, this work suggests new routes for discovering and tailoring CCCs for energy storage and many other applications.

36 MATERIALS SCIENCE↗

Ligation of Single-Site Ruthenium within Perovskite Oxides for Efficient Conversion of Thermodynamically Stable Molecules

Ru cation ligation in SrTiO 3 perovskite and their migration to the surface through exsolution are investigated for the dry reforming of methane (DRM), a chemistry that requires activation of two thermodynamically stable molecules, CH 4 and CO 2 . Compared to a supported 1 wt % Ru/SrTiO 3 benchmark, doped and exsolved Ru-SrTiO 3 demonstrate ≥3× higher CH 4 turnover rates (873 K), with isolated, ligated Ru exhibiting higher reactivity. Reactor studies assert that CH 4 and CO 2 activation are both kinetically relevant for CH 4 turnover rates on exsolved Ru-SrTiO 3 , unlike for supported Ru systems, where H-abstraction from CH 4 is the sole kinetically relevant step. As such, exsolved and doped Ru architectures are responsive toward co-reactant activation strategies, with their consequent reaction networks showing marked departures from those established for supported Ru catalysts. In situ spectroscopy and kinetic analyses propose distinct sensitivity toward CO 2 on Ru-SrTiO 3 systems, where higher CH4 turnover rates result from O-assisted C─H bond activation pathways. These pathways occur on paired Ru-oxygen vacancy sites that are inherent to the perovskite structure and are not readily accessible on supported Ru catalysts. Here, CO 2 is activated on oxygen vacancies directly adjacent to Ru active sites, which facilitates CH 4 C─H bond activation through a surface methoxy intermediate. The high reactivity of Ru-SrTiO 3 systems enables stable CH 4 turnover rates at milder reaction temperatures (673 K), conditions under which the supported counterpart, Ru/SrTiO 3 , is inactive. Overall, this work demonstrates that ligation of catalytically active cations in perovskite oxides facilitates site engineering toward atom-efficient activation of thermodynamically stable feedstocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strain Programming of Oxygen Octahedral Symmetry in Perovskite Oxide Thin Films

The collective rotations of oxygen octahedra play an important role in determining the physical properties of functional perovskite oxides. The epitaxial strain can serve as an effective means to modify the oxygen octahedral symmetry (OOS), i.e., oxygen octahedral rotation or tilt (OOR/OOT). However, the strain-OOS coupling that may alter the details of the OOS, thereby the physical properties, has not been fully understood. In this work, it is demonstrated that epitaxial strain can not only induce a structural phase transition but also precisely tune the degree of OOR. The correlated metal CaNbO 3 , which is orthorhombic, is studied by growing as epitaxial thin films. By imposing epitaxial strain, it is found that the film undergoes a structural phase transition from orthorhombic to tetragonal upon fully straining (i.e., from a + b − b − to a 0 a 0 c − ). In unstrained films, the octahedral rotation along the c-axis is as large as 15.7° that can be tuned to 6.6° by strain. This finding offers a general approach to manipulating OOR/OOT via strain engineering in complex oxide heterostructures.

36 MATERIALS SCIENCE↗

Charge doping effects on magnetic properties of single-crystal La 1-x Sr x (Cr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 )O 3 (0 ≤ x ≤ 0.5) high-entropy perovskite oxides

The observed influence of hole doping on magnetic properties is mapped for the compositionally complex high-entropy oxide ABO 3 perovskite La 1-x Sr x (Cr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 )O 3 (0 ≤ x ≤ 0.5). It is found that aliovalent A -site substitution is a viable means to manipulate the magnetically active B -site sublattice. A series of single-crystal films are synthesized and show a general trend toward stronger ferromagnetic response and a shift in magnetic anisotropy as the Sr concentration increases. Magnetometry demonstrates complex and nonuniform responses similar to rigid and uncoupled composites at intermediate dopings. This behavior points to the presence of locally inhomogeneous magnetic phase competition, where ferromagnetic and antiferromagnetic magnetic contributions create a frustrated matrix containing uncompensated spins at the boundaries between these regions. The observations are discussed in the context of known responses to hole doping in the less complex ternary LaT M O 3 (T M =Cr,Mn,Fe,Co,Ni) oxides, and they are found to be different from a simple sum of the doped parents. The results are summarized in a preliminary magnetic phase diagram.

36 MATERIALS SCIENCE↗

Exploring the potential of high entropy perovskite oxides as catalysts for water oxidation

Electrochemical water splitting is a promising technology to renewably generate hydrogen from water with no carbon footprint. However, the catalytic efficiency is hindered by the sluggishness of the oxygen evolution reaction (OER) at the anode. Therefore, developing earth-abundant, stable, and efficient OER catalysts is of keen interest. Recent studies have demonstrated that high entropy perovskite oxides (HEPOs) can exhibit superior OER activity and excellent electrochemical stability due to the synergistic effects of the multiple cations and the high entropy configuration effect. In this opinion paper, we point out the strengths and discuss the challenges and future prospects for HEPO-based electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electro-Oxidative Dehydrogenation of Ethane to Ethylene Using Lanthanum-Strontium-Iron Oxide Perovskite Electrocatalysts

Developing alternative, industrially viable ethylene production routes has received important research attention. One chemical pathway of interest is the oxidative dehydrogenation (ODH) of ethane, although issues such as product selectivity, combustion hazards, and oxidizer supply have hindered the practical scale-up of this technology. The presented work describes the use of a solid oxide fuel cell (SOFC) platform employing lanthanum-strontium-iron oxide perovskite (La 1-x Sr x FeO 3-δ , or LSFx) electrocatalysts to perform electrochemical-ODH (e-ODH), a process design that has the potential to address the challenges of ODH implementation. The effects of La and Sr stoichiometry, operating temperature, and current density are reported. The highest performance was observed using a La:Sr ratio of 0.50 (LSF0.50) at 750 °C and a current density of 0.50 A·cm –2 , achieving an ethane conversion of 18.7 ± 0.3%, ethylene selectivity of 91.4 ± 1.9%, and ethylene yield of 17.1 ± 0.1%. These results demonstrate several potential advantages for utilizing a SOFC platform to perform e-ODH of ethane to ethylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Beyond Thermal Limits: Manipulating Reactive Intermediate Coverages and Turnover Rates via Visible Photon-Mediated Catalysis on Rh-Doped Perovskite Oxides

Catalyst behavior depends on surface adsorbate energetics that are constrained by scaling relationships on metal surfaces. External stimuli (e.g., photons), however, can disrupt these limitations by modulating key intermediate coverages via non-thermal reaction pathways. Here, low-energy visible photon fluxes are utilized to selectively control coverages of strongly bound intermediates on isolated Rh active sites doped within a semiconductor perovskite oxide host (SrTiO 3 ). Red light (632 nm) facilitates selective photolytic CO desorption from rhodium gem-dicarbonyl (Rh(CO) 2 ) species that are ubiquitous reaction intermediates, including for the probe reaction studied herein CO oxidation to CO 2 . Thermochemical CO 2 formation rates (408 K) on Rh-doped SrTiO 3 are limited by adsorbed CO, exhibiting a negative apparent CO rate order (−0.6) and a positive O 2 rate order (+0.4). Arrhenius analyses, anaerobic CO oxidation measurements, and in situ spectroscopies assert that, thermochemically, lattice oxygens from the doped perovskite contribute to CO 2 formation rates. Notably, under red light illumination (0.76–2.02 W cm –2 ), the apparent CO rate order shifts to positive (+1). This, combined with decreasing apparent activation energies and CO coverages (wavelength-agnostic) with increasing photon flux, indicates that photons act selectively toward driving Rh(CO) 2 photolysis, even within complex reaction networks, thereby enhancing Rh accessibility, O 2 dissociation, and consequent rates. Finally, low-energy red light enables more stoichiometric feeds, leading to 650% higher CO 2 rates than those achieved thermally. Overall, this work elucidates how low-energy light can be leveraged, not just to improve reaction rates, but to selectively affect rates of individual elementary steps and key intermediate coverages, thereby breaking conventional scaling relationships that limit thermal catalyst performance.

catalysts↗

Tailoring electrocatalytic activity of in situ crafted perovskite oxide nanocrystals via size and dopant control

Significance The ability to scrutinize the correlation of dimension, composition, and dopant to electrocatalytic performance renders the development of highly active electrocatalysts. This work reports a general and robust strategy for crafting uniform perovskite oxide nanoparticles (i.e., BaTiO 3 and La- and Co-doped BaTiO 3 ) with controlled sizes and dopant compositions by employing amphiphilic star-like diblock copolymers as nanoreactors. Their size- and dopant-dependent oxygen reduction reaction (ORR) performances are unveiled. Particularly, La- and Co-doped BaTiO 3 nanoparticles exhibit markedly improved ORR activities over the pristine counterparts due to reduced free energy barrier of ORR and increased conductivity as substantiated by density functional theory. The nanoreactor strategy could be conveniently extended to yield various functional nanomaterials of interest with tailored sizes and compositions for electrocatalysis.

36 MATERIALS SCIENCE↗

Oxide perovskite crystals for HTSC film substrates microwave applications

The research focused upon generating new substrate materials for the deposition of superconducting yttrium barium cuprate (YBCO) has yielded several new hosts in complex perovskites, modified perovskites, and other structure families. New substrate candidates such as Sr(Al(1/2)Ta(1/2))O3 and Sr(Al(1/2)Nb(1/2))O3, Ba(Mg(1/3)Ta(2/3))O3 in complex oxide perovskite structure family and their solid solutions with ternary perovskite LaAlO3 and NdGaO3 are reported. Conventional ceramic processing techniques were used to fabricate dense ceramic samples. A laser heated molten zone growth system was utilized for the test-growth of these candidate materials in single crystal fiber form to determine crystallographic structure, melting point, thermal, and dielectric properties as well as to make positive identification of twin free systems. Some of those candidate materials present an excellent combination of properties suitable for microwave HTSC substrate applications.

Bhalla, A. S.↗

Mapping causal pathways with structural modes fingerprint for perovskite oxides

Abstract Causality is innate to the determination of the fundamental mechanism controlling any physical phenomena. However, combining causality within the standard practices of computational modelling to understand structure-functionality connections is extremely rare. This work proposes a fingerprint based on key structural modes for ABO 3 -type perovskite oxides and its derivatives, combined with causal models, for predicting Kohn–Sham energies. Our study of causal models captures the inherent coupling between structural modes such as rotation, tilt and antiferroelectric displacements, responsible for phase transition, polarization, magnetization and metal–insulator transition, exhibited by these materials. Although developed for modelling specific functionality, this method is universally applicable to derive other functionalities and even different material classes while tracking hidden causal mechanisms via structural distortions.

42 ENGINEERING↗

Single Crystal Optical Fiber and Perovskite Oxide Sensing Materials for Gas Monitoring above 500 °C

A wide range of high-value applications, including power generation and chemical manufacturing, involve harsh chemical conditions and extreme temperatures. In this work, we discuss the pairing of single crystal optical fiber with optically responsive, high-temperature stable perovskite oxide materials for monitoring of oxidizing and reduction gas streams up to 1000 °C. Optical sensing will be presented for hydrogen and oxygen monitoring in this temperature regime. Strategies will be discussed for improving stability and eliminating drift via multi-wavelength detection. The application of spatially resolved interrogation techniques, such as optical time domain reflectometry (OTDR) will be addressed for these sensors.

Wuenschell, Jeffrey↗

Exploring Ca–Ce–M–O (M = 3d Transition Metal) Oxide Perovskites for Solar Thermochemical Applications

Solar thermochemical (STC) processes hold promise as efficient ways to generate renewable fuels, fuel precursors, or chemical feedstocks using concentrated sunlight. Specifically, one actively researched approach is the two-step STC cycle, which uses a redox-active, off-stoichiometric, transition-metal oxide material to split water and/or CO 2 , generating H 2 and/or CO, respectively, or syngas (a combination of H 2 and CO). Identifying novel metal oxides that yield larger reduction extents (practically achievable off-stoichiometries) than the state-of-the-art CeO 2 is critical. Here, we explore the chemical space of Ca–Ce–M–O (M = 3d transition metal, except Cu and Zn) metal oxide perovskites, with Ca and/or Ce occupying the A site and M occupying the B site within an ABO 3 framework, as potential STC candidates. We use density functional theory (DFT)-based calculations and systematically evaluate the oxygen vacancy (VaO) formation energy (≈ enthalpy of reduction in an STC cycle), electronic properties, thermodynamic stability of CaMO 3 , CeMO 3 , and Ca 0.5 Ce 0.5 MO 3 perovskites, and the VaO formation energy within Ca 0.5 Ce 0.5 Ti 0.5 Mg 0.5 O 3 perovskite. We consider only Ca and/or Ce on the A site because of their similar size and the potential redox activity of Ce 4+ . If both Ce and M exhibit simultaneous reduction with Va O formation, the resulting perovskite could exhibit a larger entropy of reduction than a single cation reduction. The increased entropy produces increased reduction for fixed temperature, partial pressure of oxygen, and reduction enthalpy, and therefore increased STC efficiency. Importantly, we identify Ca 0.5 Ce 0.5 MnO 3 , Ca 0.5 Ce 0.5 FeO 3 , and Ca 0.5 Ce 0.5 VO 3 to be promising candidates based on their Va O formation energy and thermodynamic (meta)stability. Moreover, based on our calculated on-site magnetic moments, electron density of states, and electron density differences between pristine and defective structures, we find Ca 0.5 Ce 0.5 MnO 3 to exhibit simultaneous reduction of both Ce 4+ (A-site) and Mn 3+ (B-site), highlighting a particularly promising candidate for STC applications with a predicted higher entropy of reduction than CeO 2 . Lastly, we extract metrics that govern the trends in Va O formation energies, such as standard reduction potentials, and provide pointers for further experimental and theoretical studies, which will enable the design of improved materials for the STC cycle.

14 SOLAR ENERGY↗

Machine Learning-Guided Design of Perovskite Oxides for High-Temperature Oxygen Sensing

Presentation slides for 2025 MRS Fall Meeting & Exhibit. Reliable oxygen sensors are vital for high temperature applications including combustion engines, steel production, and petrochemical refining, yet identifying stable, high-performance materials for such environments remain challenge. We apply machine learning (ML) to predict the atmospheric oxygen partial pressure–dependent conductivity of perovskite oxides, combining data from the Materials Project and published datasets.

high temperature gas sensor↗

The influence of the 6s 2 configuration of Bi 3+ on the structures of A′BiNb 2 O 7 (A′ = Rb, Na, Li) layered perovskite oxides

Solid state compounds which exhibit non-centrosymmetric crystal structures are of great interest due to the physical properties they can exhibit. Here, the ‘hybrid improper’ mechanism – in which two non-polar distortion modes couple to, and stabilize, a further polar distortion mode, yielding an acentric crystal structure – offers opportunities to prepare a range of novel non-centrosymmetric solids, but examples of compounds exhibiting acentric crystal structures stabilized by this mechanism are still relatively rare. Here we describe a series of bismuth-containing layered perovskite oxide phases, RbBiNb 2 O 7 , LiBiNb 2 O 7 and NaBiNb 2 O 7 , which have structural frameworks compatible with hybrid-improper ferroelectricity, but also contain Bi 3+ cations which are often observed to stabilize acentric crystal structures due to their 6s 2 electronic configurations. Neutron powder diffraction analysis reveals that RbBiNb 2 O 7 and LiBiNb 2 O 7 adopt polar crystal structures (space groups I2cm and B2cm respectively), compatible with stabilization by a trilinear coupling of non-polar and polar modes. The Bi 3+ cations present are observed to enhance the magnitude of the polar distortions of these phases, but are not the primary driver for the acentric structure, as evidenced by the observation that replacing the Bi 3+ cations with Nd 3+ cations does not change the structural symmetry of the compounds. In contrast the non-centrosymmetric, but non-polar structure of NaBiNb 2 O 7 (space group P2 1 2 1 2 1 ) differs significantly from the centrosymmetric structure of NaNdNb 2 O 7 , which is attributed to a second-order Jahn-Teller distortion associated with the presence of the Bi3+ cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiple and nonlocal cation redox in Ca–Ce–Ti–Mn oxide perovskites for solar thermochemical applications

Modeling-driven design of redox-active off-stoichiometric oxides for solar thermochemical H 2 production (STCH) seldom has resulted in empirical demonstration of competitive materials. Here, we report the theoretical prediction and experimental evidence that the perovskite Ca 2/3 Ce 1/3 Ti 1/3 Mn 2/3 O 3 is synthesizable with high phase purity, stable, and has desirable redox thermodynamics for STCH, with a predicted average neutral oxygen vacancy (VO) formation energy, E v = 3.30 eV. Flow reactor experiments suggest potentially comparable or greater H 2 production capacity than recent promising Sr–La–Mn–Al and Ba–Ce–Mn metal oxide perovskites. Utilizing quantum-based modeling of a solid solution on both A and B sub-lattices, we predict the impact of nearest-neighbor composition on E v and determine that A-site Ce 4+ reduction dominates the redox-activity of Ca 2/3 Ce 1/3 Ti 1/3 Mn 2/3 O 3 . X-ray absorption spectroscopy measurements provide evidence that supports these predictions and reversible Ce 4+ -to-Ce 3+ reduction. Our models predict that Ce 4+ reduces even when it is not nearest-neighbor to the V O , suggesting that refinement of Ce stoichiometry has the possibility of further enhancing performance.

08 HYDROGEN↗