Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “cation vacancies”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 163 records · Page 9

Characterization of fluorite-structured ferroelectrics using transmission electron microscopy: Techniques, challenges, and recent advances

Fluorite-structured ferroelectrics, such as hafnium oxide and its alloyed variants, are key candidates for next-generation memory devices. Yet, fundamental questions about switching mechanisms, domain dynamics, and phase evolution remain open. Transmission electron microscopy (TEM) provides unique capabilities to address these challenges by simultaneously resolving the positions of anions and cations, chemical variations, and structural transformations. Recent advances—including in situ heating, electron beam-induced switching, electron energy loss spectroscopy, and differential phase contrast imaging—have revealed critical insights into phase transitions, potential switching pathways, and oxygen vacancy behavior. However, experimental barriers such as TEM sample-preparation-induced artifacts, high coercive fields, and imaging constraints persist, especially for polycrystalline films. By offering a focused overview of current TEM developments in fluorite ferroelectrics, this work outlines how TEM contributes to understanding key phenomena and proposes a roadmap for future studies.

36 MATERIALS SCIENCE↗

The structure, composition, and performance impact of a YSZ-GDC interdiffusion layer in solid oxide electrolysis cells

This study provides a combined experimental and computational investigation into the structure and impact of the cation interdiffusion layer that appears at the gadolinium doped ceria (GDC)/yttria stabilized zirconia (YSZ) interface in solid oxide electrolysis cells (SOECs). Scanning transmission electron microscopy (STEM) illustrates that a ∼0.4 μm interdiffusion layer (IDL) with an intermixed cation distribution and fine grain size forms upon sintering. STEM identifies that the interdiffusion layer exists in the cubic fluorite structure despite changes in cation composition. The interdiffusion layer microstructure formed during sintering does not change during SOEC testing at either 1.3V or heightened voltage pulse testing. Modeling predicts that ionic conductivity may decrease in the interdiffusion layer due to Coulombic trapping between mobile oxygen vacancies and excess Gd 3+ acceptor dopants. Yet, the density and continuous nature of the layer should benefit cell stability by substantially reducing the formation of SrZrO 3 , which is corroborated by STEM and Synchrotron X-ray diffraction (XRD). We conclude that the interdiffusion layer acts as a beneficial barrier to Sr diffusion, when operating in a regime where electrolyte void formation is not observed.

organic↗

Etching-Chemistry-Driven Ruthenium Doping on Ti 3 C 2 T x MXene for Optimizing Electrochemical Performance

We demonstrate that the etching chemistry used during MXene synthesis from Ti 3 AlC 2 MAX phase significantly influences surface functionalization and structural vacancies, which in turn affect ruthenium (Ru) ion interactions. Using hydrofluoric acid (HF) and ammonium bifluoride (NH 4 HF 2 ) as etchants, we obtained MXene surfaces with distinct functional groups and Ti vacancies that impact Ru ion interactions and electrochemical performance. Both MXene variants (labeled MX(H) and MX(N), respectively) exhibited negative zeta potentials in their pristine state, but upon the addition of Ru the zeta potential for MX(H) reached 12.9 mV while that for MX(N) remained negative at −6.4 mV. This adsorption resulted in a 14.4-fold increase in the specific capacitance of MX(H)/Ru compared to pristine MX(H), whereas MX(N)/Ru exhibited only a 4.4-fold increase over its pristine counterpart. X-ray diffraction analysis identified the formation of ammonium titanium oxide fluoride, (NH 4 ) 3 TiOF 5 , on MX(N), which likely contributed to its reduced Ru adsorption. X-ray photoelectron spectroscopy suggested the presence of Ti vacancies in both MXene variants; however, their behavior toward Ru accommodation differed markedly, with MX(H) showing the most obvious shift in the Ti 2p peak in the XPS survey spectrum, while MX(N) showed the most obvious shift in the C 1s peak. Electron paramagnetic resonance spectroscopy further demonstrated a distinct alteration in the spectral signatures of MX(H) upon Ru addition, in contrast to the negligible changes in MX(N), indicating effective passivation of the Ti defect sites in MX(H) via vacancy-assisted Ru doping. Cyclic voltammetry showed that Ru-incorporated MX(H) nanocomposites exhibit more efficient redox-active sites, as reflected in their higher capacitance values. These findings highlight the pivotal role of MXene surface chemistry in controlling cation adsorption, providing valuable insights for the rational design of high-performance electrodes.

2D surface engineering↗

Bulk Diffusion of Cl through O Vacancies in α-Cr 2 O 3 : A Density Functional Theory Study

Many metals form passive oxides which are broken or weakened by anionic-induced degradation leading to material failure and anionic diffusion is an important step of this degradation process. The diffusion of anionic species through oxides involves a combination of diffusion along grain boundaries, cracks, and channels, as well as bulk diffusion via point defects which is the focus of this study. Using density functional theory, we study bulk diffusion of Cl through O vacancies in α -Cr 2 O 3 as a model system for passive metal oxides. Little is known about Cl diffusion and bonding characteristics, so we benchmark our work through comparison to numerous studies on O diffusion in α -Cr 2 O 3 to analyze similarities and differences between the O and Cl diffusion in the passivation and degradation process of α -Cr 2 O 3 respectively. Unlike O diffusion, the lowest diffusion barrier for Cl is cross-plane diffusion between two (0001) planes through a vacant cation site but the much shorter in-plane diffusion path within the same coordination polyhedron has 35% higher barrier. This work provides the basis for considering the contributions of Cl bulk-diffusion in the overall diffusion kinetics of Cl through α -Cr 2 O 3 .

Oware Sarfo, Kofi↗

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↗

Bromine Incorporation Affects Phase Transformations and Thermal Stability of Lead Halide Perovskites

Mixed-cation and mixed-halide lead halide perovskites show great potential for their application in photovoltaics. Many of the high-performance compositions are made of cesium, formamidinium, lead, iodine, and bromine. However, incorporating bromine in iodine-rich compositions and its effects on the thermal stability of the perovskite structure has not been thoroughly studied. In this work, we study how replacing iodine with bromine in the state-of-the-art Cs 0.17 FA 0.83 PbI 3 perovskite composition leads to different dynamics in the phase transformations as a function of temperature. Through a combination of structural characterization, cathodoluminescence mapping, X-ray photoelectron spectroscopy, and first-principles calculations, we reveal that the incorporation of bromine reduces the thermodynamic phase stability of the films and shifts the products of phase transformations. Our results suggest that bromine-driven vacancy formation during high temperature exposure leads to irreversible transformations into PbI 2 , whereas materials with only iodine go through transformations into hexagonal polytypes, such as the 4H-FAPbI 3 phase. This work sheds light on the structural impacts of adding bromine on thermodynamic phase stability and provides new insights into the importance of understanding the complexity of phase transformations and secondary phases in mixed-cation and mixed-halide systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and structural characterization of the new Zintl phases Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12

Two new ternary compounds, Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12 , were synthesized and structurally characterized. The synthesis was achieved either through reactions in sealed niobium tubes or in alumina crucibles by combining the elements in excess molten Sb. Their structures were elucidated using single-crystal X-ray diffraction, and they were determined to crystallize in the orthorhombic space group Cmmm (no. 65) with the Eu 10 Cd 6 Bi 12 structure type. Akin to the archetype phase, both Mn and Zn sites contain about 25% of vacancies. Furthermore, the anionic substructure of the title phases can be described as [M 6 Pn 12 ] (M = Zn, Mn; Pn = Sb, Bi) double layers composed of the corner and edge-sharing [MPn 4 ] tetrahedra, linked by [Pn 2 ] 4– dumbbells. Eu 2+ /Yb 2+ cations fill the space between the layers, with the valence electron counts adhering closely to the Zintl–Klemm rules, i.e., both Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12 are expected to be valence-precise compounds. Analysis of the electronic structure and transport properties of Yb 10 Zn 6 Sb 12 indicate semimetallic behavior with relatively low Seebeck coefficient and resistivity that slightly decreases as a function of temperature.

36 MATERIALS SCIENCE↗

Exsolution of NiCo alloys over Ruddlesden-Popper perovskite for mild electrochemical synthesis of ammonia on protonic ceramic electrochemical cells

Ammonia synthesis from renewable energies on protonic ceramic electrochemical cells (PCECs) shows great potential. The primary challenges in ammonia synthesis on PCECs include sluggish catalytic activity, competition from the hydrogen evolution reaction, and unsatisfactory durability of the cathode, which is the active site of ammonia generation. Here, in this study, we report an elaborate design of the cathode with an intended formula of Pr 4 Ni 1.79 Co 1.2R u 0.01 O 10-δ , where NiCo alloy nanoparticles are exsolved from Ruddlesden-Popper perovskite substrates after the reduction in 5 % H 2 /Ar at 400 °C for 1 h, for electrocatalysis of the nitrogen reduction reaction to ammonia. The host material Pr 4 Ni 1.8 Co 1.2 O 10-δ with embeddable layered structure and stability was deliberately chosen to fix the Ru cation and maximize the catalytic activity of NiCo. Also, density functional theory calculations suggest that Ru doping provides an optimal balance between structural stability and redox activity, facilitating the controlled exsolution of NiCo nanoparticles and enhancing catalytic performance. As a result, the composite electrode with exsolved NiCo alloy and abundant oxygen vacancies on fuel-electrode-supported PCECs achieves a superior electrochemical activity towards ammonia synthesis: a peak ammonia formation rate of 27.84 μg h −1 cm −2 and excellent Faradaic efficiencies of 62.6 % at 350 °C.

30 DIRECT ENERGY CONVERSION↗

The Role of Cation Coordination in the Electrical and Optical Properties of Amorphous Transparent Conducting Oxides

Amorphous oxide semiconductor materials have demonstrated numerous advantages without compromise of electrical properties as compared to their crystalline counterparts, yet understanding of the fundamental principles allowing this has remained elusive. To study the origins of enhanced optoelectronic properties, we apply high-throughput, combinatorial sputtering, structural and spectral mapping, and computationally intensive ab initio molecular dynamics simulations with density functional theory to a ternary, post-transition metal oxide system, namely, zinc tin oxide. The deposited thin films exhibit a high figure of merit, achieving carrier densities in the range of 1019 to 1020 cm–3 and carrier mobilities up to 35 cm2/Vs. These results highlight the role of local distortions and cation coordination in determining the microscopic origins of carrier generation and transport. In particular, we identify the strong likelihood of Sn undercoordination in both Zn-poor and Zn-rich phases leading to the high carrier concentrations observed. This not only diverges from the still widespread historical indictment of oxygen vacancies controlling carrier population in crystalline oxides but also provides a comprehensive framework to describe the unique structure–property relationships using specific structural and electronic descriptors in disordered phase materials.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,M↗

Synthesis and structure of high-purity BaCe 0.25 Mn 0.75 O 3 : an improved material for thermochemical water splitting

Solar thermochemical hydrogen production (STCH) via redox-active metal oxides is an approach for direct solar-driven hydrogen generation typically using a high-temperature redox cycle involving refractory oxides and steam. Typical cycles involve high-temperature reduction of oxides to form oxygen vacancies, followed by lower temperature reaction between oxygen vacancies and steam where the oxide is re-oxidized and the steam is reduced to hydrogen. Only a few materials have demonstrated reversible cycling under the typically harsh STCH conditions (e.g. 1500°C reduction, 900°C re-oxidation) and critical questions remain on the true reversibility of non-stoichiometric multi-cation oxide systems, significantly hampered by the lack of single-phase samples for these material systems. To date, most STCH processes have relied on CeO 2 as a benchmark active material, but more recently, the 12R phase of BaCe 0.25 Mn 0.75 O 3 (BCM) has demonstrated greater hydrogen-generation potential at lower peak temperatures. However, previous reports of 12R-BCM have included large fractions, > 10 wt%, of secondary phases, which complicate analysis of the stability and performance. A comprehensive understanding of the redox mechanism and reversibility of the process in BCM can only be achieved with nearly single-phase samples which, to date, have been difficult to produce. Here two approaches to BCM synthesis are reported: solid state and sol–gel-based routes. It is demonstrated that both routes can be tuned to produce the 12R structure with > 97 wt% yield when annealed ≥1450°C. Herein synchrotron-based diffraction measurements of rhombohedral 12R-BCM enabled characterization of the anisotropy between thermal expansion along the c-axis and within the ab plane. The impact of high-temperature redox cycling on the stability and phase fraction of the 12R-BCM polytype was also investigated. Our results offer two viable routes for synthesis of high-purity 12R-BCM critically needed for evaluating the efficacy of BCM as a STCH material and validate its ability to split water at lower temperatures over extended numbers of redox cycles.

08 HYDROGEN↗

Mechanistic insight into copper cation exchange in cadmium selenide semiconductor nanocrystals using X-ray absorption spectroscopy

In terms of producing new advances in sustainable nanomaterials, cation exchange (CE) of post-processed colloidal nanocrystals (NCs) has opened new avenues towards producing non-toxic energy materials via simple chemical techniques. The main processes governing CE can be explained by considering hard/soft acid/base theory, but the detailed mechanism of CE, however, has been debated and has been attributed to both diffusion and vacancy processes. In this work, we have performed in situ x-ray absorption spectroscopy to further understand the mechanism of the CE of copper in solution phase CdSe NCs. The x-ray data indicates clear isosbestic points, suggestive of cooperative behavior as previously observed via optical spectroscopy. Examination of the extended x-ray absorption fine structure data points to the observation of interstitial impurities during the initial stages of CE, suggesting the diffusion process is the fundamental mechanism of CE in this system.

74 ATOMIC AND MOLECULAR PHYSICS↗

Design of Next-Gen Cathode Materials With Both Cation and Anion Redox

Among all candidates of positive electrode materials for lithium ion batteries, the lithium rich layered oxides have gained growing research interests in recent years. Their energy density can reach closely to 700-900Wh/g (at materials level), making them the positive electrode materials with highest energy density among all known intercalation compounds for cathode materials. Combining both first principles computation, advanced electron and X-ray based imaging, we demonstrated that in the Li-rich materials oxygen vacancies are present and assist the transition metal ion migration through a facile mechanism. This means it is critically important to control the oxygen activities in these compounds for high voltage operations. In addition, the NiMn spinel oxides show little oxygen activities and under optimized synthesis condition the electrolyte/electrode interface showed superior stability. Combining the strengths of materials synthesis and the advanced characterization, I will discuss in details the strategies for stabilizing the anion redox for higher voltage electrode materials for lithium ion batteries.

Meng, Ying Shirley↗

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↗

Elucidating Structural Transition Dynamics in the Magnesium Cathode MgCr 2 O 4

Multivalent batteries, e.g., those based on magnesium (Mg), are promising candidates for next-generation energy storage due to their high volumetric energy densities and low cost. However, the corresponding ion migration and structural transition mechanisms are often linked and difficult to observe directly. Here, in this paper, we report the direct investigation of atomic transport pathways of cations in spinel magnesium chromate (MgCr 2 O 4 ) by using aberration-corrected scanning transmission electron microscopy (STEM). Cr atoms are directly observed to reversibly occupy the otherwise vacant octahedrally coordinated interstitial sites, passing through tetrahedral sites normally occupied by Mg. Furthermore, imaging and electron energy loss spectroscopy show that electron irradiation induces the formation of Mg and O vacancies, facilitating the migration of Cr and leading to an irreversible phase transition. These results demonstrate the ability of STEM to capture the pathway of deleterious point defects that can result in undesirable phase transitions.

25 ENERGY STORAGE↗

Nanoscale interplay of native point defects near Sr-deficient SrxTiO 3 /SrTiO 3 interfaces

SrTiO 3 has many applications involving interfaces with other materials, but defects that affect the properties of SrTiO 3 films can also play a significant role at its heterointerfaces and even at junctions with nonstoichiometric SrTiO 3 . Depth-resolved cathodoluminescence spectroscopy (DRCLS) combined with systematic cation Sr content reduction in SrxTiO 3 ultrathin films grown on SrTiO 3 showed an interplay of native point defects and electronic structure within the Sr-deficient film and how interplay extends tens of nanometers into the substrate below. Understanding how defects form and affect interface electronic structure during epitaxial growth is central to improving complex oxide devices. Controlling the balance of oxygen vacancy defects with strontium vacancies and other acceptor-like defects can improve control over free carrier densities. Likewise, control over nanoscale defect charge distributions can advance new device features such as two-dimensional hole gases and the performance of existing devices such as ferroelectric tunnel junctions. This study shows how DRCLS directly measures the relative densities and spatial distributions of multiple native defects within and extending away from nanoscale SrxTiO 3 /SrTiO 3 junctions and how their interplay varies with controlled epitaxial growth. In turn, these growth-dependent defect variations can help guide SrTiO 3 epitaxial growth with other complex oxides.

36 MATERIALS SCIENCE↗

Computationally Accelerated Discovery of High Entropy Pyrochlore Oxides

High entropy ceramics provide enhanced flexibility for tailoring a wide range of physical properties, emerging from the diverse chemical and configurational degrees of freedom. Expanding upon the endeavors of recently synthesized high entropy ceramics in rock salt, fluorite, spinel, and perovskite structures, we explore the relative feasibility of formation of high entropy pyrochlore oxides, A 2 B 2 O 7 , with multication occupancy of the B-site, estimated from first-principles-based thermodynamic descriptors. Subsequently, we used Monte Carlo simulations to estimate the phase composition, oxygen vacancy concentration, and local ionic segregation as a function of temperature and oxygen partial pressure. In synergy with the theoretical calculations, we have investigated the synthesis of several multicomponent oxides with a pyrochlore composition, related to our computational investigations, resulting in four phase pure and one 97.4% pure high entropy pyrochlore oxides. Ultimately, our approach allows us to evaluate potential impurity phases, ionic disorder, and oxygen vacancy concentration in response to the experimental variables, thereby making realistic predictions that can direct and accelerate experimental synthesis of novel multicomponent ceramics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Iodine Close Packing in Hybrid Halide Bismuth(III) and Antimony(III) Semiconductors: (NH 3 (CH 2 ) 7 NH 3 ) 2 Bi 2 I 10 and (NH 3 (CH 2 ) 7 NH 3 ) 2 Sb 2 I 10

Simple features in complex hybrid inorganic–organic crystalline materials provide opportunities for targeted discovery of materials with desired optoelectronic properties. In this study, we report the structure and optoelectronic properties of isostructural (NH 3 (CH 2 ) 7 NH 3 ) 2 Bi 2 I 10 and (NH 3 (CH 2 ) 7 NH 3 ) 2 Sb 2 I 10 . The crystal structures are characterized by corner-connected metal-iodide octahedral chains that form a cubic close-packed iodine inorganic framework. Variable temperature UV–visible diffuse reflectance spectroscopy reveals stark contrasts in the onset of absorption and color changes between the [MX6]3– based structures, due to differences in the interaction of the (NH 3 (CH 2 ) 7 NH 3 ) 2+ organic ammonium cation and the iodine packing of the inorganic framework. Density functional theory (DFT) calculations reveal flat bands reflective of the pseudo-1D crystal structure. Dark microwave conductivity (DMC) and time-resolved microwave conductivity (TRMC) reveal an excitonic character with long carrier lifetimes, consistent with the electronically confined octahedral chains. Comparison of the structural features with those of other diammonium-containing crystals reveals that diammoniumheptane can substitute into structures, displacing inorganic octahedra while retaining a close-packed anion framework. This provides a means for targeting new hybrid materials in which “vacancy-ordering” provides a crystal chemical approach for targeting desirable optoelectronic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective reduction in epitaxial SrFe 0.5 Co 0.5 O 2.5 and its reversibility

Oxygen-vacancy engineering in transition metal oxides enables programmable functionalities by modulating the valence states and local coordination of constituents. Here, we report the selective reduction of cobalt ions in epitaxial SrFe 0.5 Co 0.5 O 2.5 thin films under reducing gas environments, while iron ions remain unchanged. X-ray absorption spectroscopy reveals an absorption edge shift of 1.65 eV in the Co L-edge upon reduction, and multiplet simulations estimate a decrease in the average Co valence from Co 2.91+ to Co 2.00+ . This site- and element-specific reduction leads to the formation of a structurally distinct oxygen-deficient phase stabilized by oxygen vacancies at tetrahedral sites, as confirmed by density functional theory. Optical spectroscopy reveals an increase in the bandgap from 2.47 eV to 3.04 eV, accompanied by enhanced transparency. Furthermore, simultaneous in situ diffraction and transport measurements confirm fully reversible redox-driven transitions among three phases: reduced defective perovskite, brownmillerite, and oxygen-rich perovskite phases. These findings demonstrate that selective redox control in multi-cation oxides enables the realization of chemically and functionally distinct oxygen-deficient phases.

Fuel cells↗