Difference In Ionic Radii Research Articles

Tailoring breakdown strength and energy-storage performance of silicon-integrated lead-free epitaxial BZT thin films through multi-element B-site substitutions

Developing high-temperature dielectric thin films with high-performance energy-storage properties for harsh environment applications has received increased attention. Herein, a multi-element co-doping strategy is proposed to enhance the breakdown strength and energy storage properties of lead-free BaTiO3-based thin films, which were deposited on silicon substrates using pulsed laser deposition. Due to the difference in ionic radii and valence states between the multi-dopants and host Ti-cations, the local lattice distortion and local charged defects are induced, which results in the reduction in the size of polar nanoregions (PNRs) and weakened coupling interactions between these PNRs, thus achieving stronger breakdown strength (EBD). Accordingly, owing to an enhanced EBD of 7.8 MV/cm and a delayed polarization saturation, a superior recoverable energy-storage density (Ur) of 140.8 J/cm3 along with an excellent energy efficiency (η) of 93.2 % were achieved at room temperature in the multi-element doped Ba(Zr0.2Ti0.2Mn0.2Nb0.2Sm0.2)O3 (BZTMNS) thin film. Moreover, the BZTMNS thin film also exhibits an excellent Ur of 102.6 J/cm3, a good η of 86.4 %, and a high EBD of 6.6 MV/cm at an operating temperature of 200 °C. Additionally, a small fluctuation of Ur (-6.1 %) and η (-11.7 %) values can also be observed in BZTMNS thin film in high cycling endurance, up to 1010 cycles, even when operated at an elevated temperature of 200 °C. These findings in the BZTMNS thin film demonstrate a feasible way to design high-temperature capacitors for modern electronic devices for hybrid vehicles and underground oil/gas explorations.

Softening of the optical phonon by reduced interatomic bonding strength without depolarization.

Softening of the transverse optical (TO) phonon, which could trigger ferroelectric phase transition, can usually be achieved by enhancing the long-range Coulomb interaction over the short-range bonding force1, for example, by increasing the Born effective charges2. However, it suffers from depolarization effects3,4 as the induced ferroelectricity is suppressed on size reduction of the host materials towards high-density nanoscale electronics. Here, we present an alternative route to drive the TO phonon softening by showing that the abnormal soft TO phonon in rocksalt-structured ultrawide-bandgap BeO (ref. 5) is mainly induced by a substantial reduction in the short-range bonding interaction due to the Be-O bond stretching caused by an electron cloud-overlap-induced Coulomb repulsion between two adjacent oxygen ions that are arranged octahedrally around an extremely small Be ion. We further demonstrate the emergence of robust ferroelectricity in strain-induced perovskite BaZrO3 and ultrathin HfO2 and ZrO2 films6,7 grown epitaxially on lattice-mismatched SiO2/Si substrate arising from the softening of the TO phonon driven by a reduction in the short-range bonding strength of biaxial strain-induced stretching bonds. These findings shed light on developing a unified theory for ferroelectricity enhancement in ultrathin films free from depolarization fields by tailoring chemical bonds using ionic radius differences, strains, doping and lattice distortions.

An in-depth comparison of dielectric, ferroelectric, piezoelectric, energy storage, electrocaloric, and piezocatalytic properties of Ba0.92Ca0.08Zr0.09Ti0.91O3 and Ba0.92Ca0.08Sn0.09Ti0.91O3 piezoceramics

The futuristic technology demands materials exhibiting multifunctional properties. Keeping this in mind, an in-depth investigation and comparison of the dielectric, ferroelectric, piezoelectric, energy storage, electrocaloric, and piezocatalytic properties have been carried out on Ba0.92Ca0.08Zr0.09Ti0.91O3 (BCZT) and Ba0.92Ca0.08Sn0.09Ti0.91O3 (BCST) lead-free compounds synthesized through the conventional solid state reaction method. Further, the Rietveld refinement against the XRD patterns affirmed the coexistence of orthorhombic (Amm2) and tetragonal (P4mm) phases at room temperature for both compounds. While BCZT compound demonstrated remarkable dielectric, piezoelectric, and piezocatalytic characteristics with maximum dielectric constant () ≈ 13304 near the Curie temperature ( ≈ 105 °C), converse piezoelectric coefficient ≈ 609 pm V-1 , power density () ≈ 89.71 KW cm-3 at room temperature, and 82.7 % Rhodamine B (RhB) dye degradation capability; on the other hand, BCST compound exceled in superior energy storage density () ≈ 191.8 mJ cm-3 with efficiency η ≈ 73.26% near room temperature and enhanced electrocaloric properties with adiabatic temperature change ≈ 0.980 K, isothermal entropy change ≈ 1.15 J Kg-1K-1 and a higher electrocaloric responsivity ) ≈ 0.49 K mm kV-1. These distinctions arise from the difference in ionic radii, lattice distortion, and the electronic configurations of the dopant ions, leading to a greater polarization change and a lower coercive electric field in the BCST ceramic. The outcome of the present study provides valuable insights for selecting a dopant tailored compound for specific application and underscores the potential of such ceramics in energy storage, piezocatalysis, and the development of advanced solid-state cooling devices for future applications.

Strain-Driven Phase Transitions in Delafossite Cu1-xAxAlO2: A Key to Enhanced Photo(electro)catalytic Performance.

This study investigates the impact of intrinsic strain and phase transitions on the thermodynamic stability and electronic properties of Cu1-xAxAlO2 solid solutions, which are key to their photocatalytic performance. It is demonstrated that Cu1-xAxAlO2 with A = Ag, Au, Pt can form continuous isostructural solid solutions due to relatively small compressive strain, while a substantial increase strain restricts Cu1-xPdxAlO2 to forming only limited solutions. For A = Li, Na, the formation of heterostructural solid solutions is facilitated by structural motif alterations, accommodating significant differences in ionic radii and A-O bond characteristics. Specifically, Cu1-xLixAlO2 exhibits a phase transition at x ≈ 0.333, whereas Cu1-xNaxAlO2 undergoes three distinct phase transitions. Electronic structure analysis indicates that in Cu1-xAxAlO2 (A = Ag, Au), d10-d10 closed-shell interactions dominate, enabling tunable band gaps with varying solubility. Nevertheless, increased intrinsic strain in metal sublattices, as seen in A = Pd and Pt, shifts antibonding states to the Fermi level, inducing a semiconductor-to-metal transition. Experimental evidence confirms that Ag+ ions modulate the band gaps and carrier dynamics in Cu1-xAgxAlO2, with Cu0.75Ag0.25AlO2 exhibiting heightened photoelectrochemical activity and a 38.5-fold enhancement in H2 production rate over CuAlO2. Additionally, the coordination environment changes between alkali metals and O, induced by phase transitions, effectively tune the band edge positions and carrier dynamics of Cu1-xAxAlO2 (A = Li, Na) heterostructural solid solutions. Therefore, 3R-Cu0.97Li0.03AlO2 with asymmetric nonlinear dumbbell O-Cu-O demonstrates the highest photocatalytic H2 production activity, 72.9 times greater than CuAlO2. In contrast, α-Cu1-xAxAlO2 with a smaller CuO6 octahedral splitting energy exhibits increased band gaps, resulting in diminished photocatalytic activity. This research underscores that strain-driven phase transition provides an additional control factor and new mechanism for regulating the photo(electro)catalytic activity of Cu1-xAxAlO2 solid solutions.

In Situ Vanadium Modification Induced a Back Interfacial Field Passivation Effect toward Efficient Kesterite Solar Cells beyond 11% Efficiency.

Realization of a high-quality back electrode interface (BEI) with suppressed recombination is crucial for Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. To achieve this goal, the construction of a traditional chemical passivation effect has been widely adopted and investigated. However, there is currently a lack of reports concerning the construction of a field passivation effect (FPE) for the BEI. Herein, considering the characteristic of the negligible difference in ionic radius between Mo (0.65 Å) and V (0.64 Å) as well as the presence of one less valence electron compared to Mo, vanadium (V) was employed and in situ incorporated into the MoSe2 interfacial layer during the deposition of the Mo:V electrode and selenization process. This allowed for the establishment of a desirable in situ VI-FPE interface with p-MoSe2:V/p-CZTSSe at the BEI. The p-type characteristic in MoSe2:V is attributed to the presence of the VMo acceptor; notably, the Fermi energy level of MoSe2:V has shifted downward by 0.62 eV compared to MoSe2, thereby facilitating the formation of an optimized band alignment between MoSe2:V and the absorber. Consequently, the photovoltaic parameters of the cell-FPE have experienced a significant increase due to the enhanced carrier transportation efficiency compared to cell-ref, resulting in a remarkable improvement in efficiency from 8.28 to 11.11%.

High-Performance Tin Oxide Thin-Film Transistors Realized by Codoping and Their Application in Logic Circuits.

Tin oxide is a promising channel material, offering the advantages of being low-cost and environmentally friendly and having a wide band gap. However, despite the high electron mobility of SnO2 in bulk, the corresponding thin-film transistors (TFTs) generally exhibit moderate performance, hindering their widespread application. Herein, we proposed a codoping strategy to improve both the electrical property and the stability of SnO2 TFTs. A comparative analysis between doped and undoped SnO2 was conducted. It is observed that taking advantage of the difference in ionic radii between two dopants (indium and gallium) and the tin ions in the host lattice can effectively reduce impurity-induced strain. Additionally, we investigated the effect of codoping content on SnO2 TFTs. The optimal codoped SnO2 (TIGO) TFTs demonstrate high performance, featuring a field-effect mobility of 15.9 cm2/V·s, a threshold voltage of 0.2 V, a subthreshold swing of 0.5 V/decade, and an on-to-off current ratio of 2.2 × 107. Furthermore, the devices show high stability under both positive and negative bias stress conditions with a small threshold voltage shift of 1.8 and -1.2 V, respectively. Utilizing the TIGO TFTs, we successfully constructed a resistor-loaded unipolar inverter with a high gain of 10.76. This study highlights the potential of codoped SnO2 TFTs for advanced applications in electronic devices.

A novel magnesium reduction technique for the separation of ytterbium from non-aqueous solutions

The separation of heavy rare earth elements, particularly Tm, Yb, and Lu, poses significant challenges due to their small differences in ionic radii and close chemical properties. Utilizing the variable valence properties of ytterbium can simplify the separation from adjacent elements. Therefore, a novel magnesium reduction technique was proposed, offering selective reduction and separation of ytterbium. In comparison to traditional methods such as sodium amalgam reduction and mercury cathode reduction, this approach achieves efficient separation of ytterbium and lutetium without the need for mercury, rendering it more environmentally friendly and safe. Under a non-oxidizing nitrogen atmosphere, utilizing magnesium powder as the reducing agent and a mixed solution of 1,4-dioxane and ethanol as the reaction solvent, only 20 min are required to complete one reduction-precipitation operation for simulated solutions. This yields a recovery of 70.89% and a purity of 97.5% for ytterbium (II) chloride. The optimal experimental conditions obtained are applied to natural heavy rare earth mixed solutions, resulting in the recovery of over 90% of ytterbium after three reduction-precipitation processes. Post-ytterbium separation, the residual solution is enriched with approximately three times the amount of thulium and lutetium, greatly facilitating subsequent separation processes. This method liberates ytterbium reduction-separation from dependence on mercury, offering not only rapid and efficient processing but also significant industrial prospects.

Analysis of Optical Temperature Sensing Performance of Alkali Metal Doped Na0.5Gd0.5TiO3: Yb, Er Based on Judd‐Ofelt Theory and First Principles Calculations

AbstractIn alkali metal‐doped optical temperature measurement materials, the influence of the electronegativity difference of alkali metal ions on optical temperature measurement performance is rarely reported. This study investigates and analyzes the performance of optical temperature measurement of Na0.5Gd0.5TiO3: Yb, Er doped with Li+ and K+ ions, utilizing the Judd‐Ofelt theory and the first‐principles method. The results reveal that the sensitivities increase with the increase of atomic number of doped alkali metal ions. The reason is that a difference in ionic radius between the dopant and the replaced ion decreases the symmetry of the crystal field and increases the value of Ω2. The doping K+ with low electronegativity leads to an increase in the s orbital electron density of rare earth ions, thereby repelling the d orbital electrons, reducing the d electron density, and decreasing the value of Ω6. Based on the Judd‐Ofelt theory, a combination of a large Ω2 and a small Ω6 is expected to enhance the absolute sensitivity of optical temperature‐measuring materials doped with rare earth ions. Therefore, it can be concluded that doping an ion with low electronegativity and a significant radius difference from the substitution site is beneficial for enhancing the optical temperature sensitivity.

Scaling high-speed counter-current chromatography for preparative neodymium purification: Insights and challenges

Efficient rare earth element (REE) separations are becoming increasingly important to technologies ranging from renewable energy and high-performance magnets to applied radioisotope separations. These separations are made challenging by the extremely similar chemical and physical characteristics of the individual elements, which almost always occupy the 3+ oxidation state under ambient conditions. Herein, we discuss the development of a novel REE separation aimed at obtaining purified samples of neodymium (Nd) on a multi-milligram scale using high-speed counter-current chromatography (HSCCC). The method takes advantage of the subtle differences in ionic radii between neighboring REEs to tune elution rates in dilute acid through implementation of the di-(2-ethylhexyl)phosphoric acid (HDEHP)-infused stationary phase (SP) of the column. A La/Ce/Nd/Sm separation was demonstrated at a significantly higher metal loading than previously accomplished by HSCCC (15 mg, RNd/REE > 0.85), while the Pr/Nd separation was achieved at lower metal loadings (0.3 mg, RNd/Pr = 0.75 – 0.83). The challenges associated with scaling REE separations via HSCCC are presented and discussed within.

Enthalpy of mixing of solid solution rhomboclase – Indium-substituted rhomboclase (H3O) Fe1−xInx(SO4)2·nH2O

Solid solution of rhomboclase [nominally (H3O) Fe(SO4)2·3H2O] with Fe-In substitution was synthesized by coprecipitation and hydrothermal treatment and investigated by chemical, X-ray diffraction, and thermodynamic analysis in this study. The solid solution is continuous over the whole stoichiometric range despite significant differences in ionic radii between Fe3+ and In3+. Enthalpy of formation of rhomboclase and enthalpies of mixing of solid solution rhomboclase – indium-substituted rhomboclase were determined by acid-solution calorimetry in 5 mol·dm−1 HCl at T = 298.15 K and p = 1 bar. The actual compositions of the studied synthetic end members are (H3O)0.798Fe(SO4)1.899·3.078H2O (rhomboclase with molecular mass of 308.8719 g·mol−1) and (H3O)1.067In(SO4)2.034·3.017H2O (indium-substituted rhomboclase with molecular mass of 384.8377 g·mol−1). The enthalpies of mixing were obtained for a series of four indium-incorporating rhomboclase synthetic samples with molar In/(In + Fe) ratios of 0.115, 0.226, 0.537, and 0.733. The enthalpy of formation from elements in their standard state at T = 298.15 K and p = 1 bar obtained in this study by thermochemical cycle for (H3O)0.798Fe(SO4)1.899·3.078H2O is: ΔfH298.15°=-2815.2±2.8 kJ·mol−1. Mean measured enthalpies of dissolution for (H3O)0.798Fe(SO4)1.899·3.078H2O and (H3O)1.067In(SO4)2.034·3.017H2O are: ΔdissH°=14.47±0.42 kJ·mol−1 and -6.68±0.27 kJ · mol−1, respectively. Enthalpies of mixingΔmixH° have small positive values and can be fitted by a regular solid solution model with a mixing parameter W=4.26±0.32 kJ·mol−1.

Tuning structural, dielectric, and ferroelectric properties of BTO-based ceramics through dual-site substitution

Different strategies for tuning the properties of ferroelectric materials have been employed for advancing electromechanical applications. Among several material synthesis techniques explored, site substitution is an effective approach. The present work focuses on Ba1-xCaxSnyTi1-yO3 (BCST) ceramics prepared by solid-state sintering route with different substitution levels (x = 0, 0.05 and y = 0, 0.09). The impact of site substitution on the properties of Barium Titanate (BTO), phase purity, structural analysis, chemical composition, dielectric, and ferroelectric properties have been studied. An ionic radii difference at A-site and B-site substitution is a key factor to achieve significant changes in physical and structural properties. X-ray diffraction patterns ensure the formation of pure phase perovskite structure in all the compositions. Raman spectroscopy indicates Ca substitution not only occurs at the A-site but also within the oxygen octahedra, adversely affecting the properties. Ca and Sn act as strong grain growth inhibitors, leading to a fine-grained and dense microstructure in BCST. While Ca substitution has a limited impact on the Curie temperature (TC), Sn substitution lowers TC in BST (54 °C) and BCST (50 °C) compared to BTO (126 °C). The Sn substitution results in the coexistence of multiple phases (rhombohedral, tetragonal and orthorhombic) in BST, enhancing its properties (ε' = 6118 at RT, Pr = 5.50 μC/cm2, Q11 = 0.060 m4/C2, d*33 = 526 pm/V) in comparison to BTO. These results acknowledge the role of substituents in lattice disruption, paving the way for chemistry-based materials design in the field of dielectric, actuator and energy storage applications.

One-Step Preparation of High-Stability CsPbX3/CsPb2X5 Composite Microplates with Tunable Emission.

The core-shell structure is an effective means to improve the stability and optoelectronic properties of cesium lead halide (CsPbX3 (X = Cl, Br, I)) perovskite quantum dots (QDs). However, confined by the ionic radius differences, developing a core-shell packaging strategy suitable for the entire CsPbX3 system remains a challenge. In this study, we introduce an optimized hot-injection method for the epitaxial growth of the CsPb2X5 substrate on CsPbX3 surfaces, achieved by precisely controlling the reaction time and the ratio of lead halide precursors. The synthesized CsPbX3/CsPb2X5 composite microplates exhibit an emission light spectrum that covers the entire visible range. Crystallographic analyses and density functional theory (DFT) calculations reveal a minimal lattice mismatch between the (002) plane of CsPb2X5 and the (10) plane of CsPbX3, facilitating the formation of high-quality type-I heterojunctions. Furthermore, introducing Cl- and I- significantly alters the surface energy of CsPb2X5's (110) plane, leading to an evolutionary morphological shift of grains from circular to square microplates. Benefiting from the passivation of CsPb2X5, the composites exhibit enhanced optical properties and stability. Subsequently, the white light-emitting diode prepared using the CsPbX3/CsPb2X5 composite microplates has a high luminescence efficiency of 136.76 lm/W and the PL intensity decays by only 3.6% after 24 h of continuous operation.

Optoelectronic and mechanical properties of gallium arsenide alloys: Based on density functional theory

First principles calculations based on density functional theory (DFT) were performed to investigate the structural, electronic, optical and mechanical properties of pristine GaAs compound and its alloy; Ga0.75Al0.25As, Ga0.75In0.25As, Ga0.75Sn0.25As, Ga0.75Ti0.25As. WIEN2K and Quantum expresso (QE) codes were adopted for calculations using generalized gradient approximation (GGA) in Perdew-Burke Erzenhoff (PBE) as exchange correlation function for both codes. Full potential linear augmented plane wave (FPLAPW) with the local orbital method was adopted as implement in WIEN2K code. In QE code, norm-conserving pseudopotentials were employed on a plane-wave expansion of the wave functions. Structural and electronic properties were elaborated since their result gives information about the optical and mechanical performance. Electronic band structure and optical parameters were performed using WIEN2K code. Underestimation of band gap observed from DFT calculations were corrected by using Modified Becke and Johnson (mBJ). Mechanical components were determined using QE with thermo_pw package. Lattice constant, volume, bulk modulus and other physical parameters were calculated for structural properties. Discrepancy in these parameters as observed in crystal structure is associated to difference in ionic radius of host and substituted atom. The results of band structure and density of states were calculated for electronic properties. All the studied compounds were semiconductors in nature except Ga0.75Sn0.25As which displayed metallic character. Optical parameters including extinction coefficient, absorption coefficient, refractive index, optical conductivity, optical reflectivity and energy loss function have been computed from the dielectric function at energy range of 0 to 25 eV using the Kramers-Kronig transformations. Calculated elastic function were used to compute the mechanical properties such as anisotropic, brittle characteristics, stiffness and many others. All the results were compared with available theoretical and experimental records.

Influence of doping elements on thermo-physical properties of co-doped strontium zirconate for potential thermal barrier coatings

Strontium zirconate is a promising material for thermal barrier coatings due to some excellent properties. New four co-doped strontium zirconate with lower thermal conductivity and higher thermal expansion coefficient were synthesized in this study. Sr(Zr0.9Y0.05Yb0.05)O2.95 (SZYYb) with the smallest difference in ionic radius and mass has lowest thermal diffusion coefficients mainly due to the effect of extrinsic phonon scattering mechanisms, including lattice distortion and grain size. The electronic structures of four co-doped SrZrO3 were analyzed by first-principles calculations. The findings suggested that the difference in bond strength caused by different doping affected the differences in the lattice constant, which led to the highest thermal expansion coefficient of SZYYb.

Improvement of H2O2 electrogeneration using a Vulcan XC72 carbon-based electrocatalyst modified with Ce-doped Nb2O5

The use of the oxygen reduction reaction (ORR) for in-situ production of H2O2 is an attractive alternative to replace the methods based on anthraquinone oxidation. This study investigates the modification of Vulcan XC72 carbon with Ce-doped Nb2O5 in different molar proportions and its application as electrocatalysts in the ORR. One performed the characterization of the electrocatalysts using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, contact angle measurements, and X-ray photoelectron spectroscopy. Subsequently, the electrocatalysts were analyzed for the ORR, and the Nb2O5 doped with 0.5 % Ce showed the highest electrocatalytic response. This electrocatalyst was also employed as a gas diffusion electrode and exhibited more significant H2O2 production at all potentials than the Vulcan XC72 carbon modified solely with Nb2O5. At the applied potentials of −1.3 V and −1.9 V, it produced 105 % and 86 % more H2O2, respectively, than the Vulcan XC72 carbon modified only with Nb2O5. These results can be attributed to the doping of Nb2O5 with 0.5 % Ce, which induces local distortions in the crystal lattice of Nb2O5 due to the difference in ionic radius between Nb5+ and Ce3+, combined with increased hydrophilicity and wetting properties, may have facilitated electron transfer and O2 transport, favoring the ORR.

Highly selective capture of cesium using an electrochemically renewable molybdenum-based crystalline adsorbent

The development of highly efficient adsorbents for the capture of 133Cs and the removal of radioactive isotope 137Cs from complex aqueous solutions is crucial for the chemical production and environmental remediation. Herein, Mo-based crystalline adsorbent with sub-nanometer (5.76 Å) channels was successfully prepared and used in electrochemically controlled Cs+ separation process. Crystalline structures of MoIC (HNO3) before and after adsorption of Cs+ were clearly elucidated using powder X-ray diffractometer (PXRD). A more environmentally friendly electrochemical method was employed to achieve easy release and recapture of Cs+. Adsorption comparison experiments revealed that our material clearly outperforms the reported adsorbents for the removal or recovery of trace amount of Cs+ (< 10 mg L−1). Furthermore, MoIC (HNO3) also exhibited excellent selectivity for low concentration of Cs+ over highly excess of competitive cations, such as Mg2+, Ca2+ and K+, which are commonly distributed in brines. The maximum separation factors of Cs+/Mg2+, Cs+/Ca2+ and Cs+/K+ are 1.2 × 105, 1.3 × 104 and 66, respectively. The remarkable selectivity can be attributed to the outstanding ion-sieving ability of sub-nanometer channels based on the differences in ionic radius and hydration energy of these cations. A real brine was introduced to further prove that one complete cycle of electrochemical adsorption and desorption can dramatically reduce the competing ions concentrations up to 980 times. We anticipate that our findings may give the prospect of opening up new path for the efficient separation of Cs+ from brines using molybdenum-based adsorbent via electrochemically controlled process as a green and sustainable way.

High-pressure synthesized perovskite-type CeTaN&lt;sub&gt;2&lt;/sub&gt;O and its magnetic and electrical properties

Recently, it has been discovered that the &lt;i&gt;AB&lt;/i&gt;(N,O)&lt;sub&gt;3&lt;/sub&gt;-type perovskite oxynitrides exhibit excellent dielectric, ferroelectric, and photocatalytic properties, promising for applications in the fields of optoelectronics, energy storage, and communication. Due to the differences in charge, ionic radius, and covalent bonding between N&lt;sup&gt;3–&lt;/sup&gt; ion and O&lt;sup&gt;2–&lt;/sup&gt; ion, the N substitution for O enhances the &lt;i&gt;B&lt;/i&gt;(N,O)&lt;sub&gt;6&lt;/sub&gt; octahedron tilting, giving rise to exotic properties and functionalities. However, the current fabrication process for this type of material is rather time-consuming, leading to products with an appreciable quantity of impurities. In this study, using oxide precursors and sodium amide as the nitrogen source, high-purity perovskite-type oxynitride CeTaN&lt;sub&gt;2&lt;/sub&gt;O bulk materials are successfully synthesized under high-temperature and high-pressure conditions provided by a cubic-anvil press. The synthesis time decreases to 1 h, achieving rapid production. The lattice structure and physical properties of the obtained samples are comprehensively investigated. X-ray powder diffraction experiments and subsequent Rietveld refinement indicate that the title material shows an orthorhombic crystal structure with the space group of &lt;i&gt;Pnma&lt;/i&gt;. The X-ray absorption spectra confirm the charge configuration and the anion composition as Ce&lt;sup&gt;3+&lt;/sup&gt;Ta&lt;sup&gt;5+&lt;/sup&gt;N&lt;sub&gt;2&lt;/sub&gt;O. Magnetization and specific heat measurements reveal that the exchange interactions are mainly antiferromagnetic, with a potential magnetic transition below 2 K. The electrical transport data demonstrate typical semiconductor behaviors, which can be further explained by a three-dimensional variable-range hopping model. Our study paves the way for putting this exotic perovskite oxynitride into practical applications.

Modulating the effective ionic radii of trivalent dopants in ceria using a combination of dopants to improve catalytic efficiency for the oxygen evolution reaction.

Aliovalent doping in ceria and defect engineering are important aspects in tuning the properties of ceria for advanced technological applications, especially in the emerging field of electrocatalytic water-splitting for harvesting renewable energy. However, the ambiguity regarding the choice of dopants/co-dopants and ways to deal with the size difference between dopants and lattice hosts remains a long-standing problem. In this study, ceria was aliovalently codoped with Sc3+ and La3+ while keeping the total concentration of dopants constant; the ionic radius of the former is smaller and that of the latter is larger than Ce4+. Variations in the relative amounts of these dopants helped to modulate the effective ionic radii and match that of the host. A systematic study on the role of these aliovalent dopants in defect evolution in ceria and in modulating the Ce3+ fraction using powder XRD, Rietveld refinement, positron annihilation lifetime spectroscopy, X-ray photoelectron spectroscopy, Eu3+ photoluminescence, and Raman spectroscopy is presented here. The evolved defects and their dependence on subtle factors other than charge compensation are further correlated with their electrocatalytic activity towards oxygen evolution reaction (OER) in alkaline medium. The catalyst with an optimum defect density, maximum Ce3+ fraction at the surface and the least effective ionic radius difference between the dopants and the host demonstrated the best performance towards the OER. This study demonstrates how effective ionic radius modulation in defect-engineered ceria through a judicious choice of codopants can enhance the catalytic property of ceria and provides immensely helpful information for designing ceria-based heterogeneous catalysts with desired functionalities.

A novel dual-phase high-entropy (La0.2Nd0.2Gd0.2Er0.2Yb0.2)2Zr2O7 ceramic for thermal barrier coatings applications: Preparation, microstructure, and thermo–physical properties

High-entropy rare earth zirconates (RE2Zr2O7) have attracted significant research attention for thermal barrier coatings (TBCs) application due to their superior performance. However, currently used high-entropy RE2Zr2O7 shows only the modest improvements, thus limiting their overall performance enhancement. Therefore, novel high-entropy RE2Zr2O7 (La0.2Nd0.2Gd0.2Er0.2Yb0.2)2Zr2O7 (HEC) was synthesized in this study by chemical co-precipitation method, which was characterized by dual-phase and significant differences in ionic radius and atomic mass. Compared with single-component RE2Zr2O7 (RE = La, Nd, Gd, Er, and Yb) ceramics, HEC demonstrates significantly superior performance, including higher hardness (11.705 GPa), fracture toughness (1.693 MPa m1/2), and thermal expansion coefficient (11.1926 × 10−6/K, 1400 °C), and lower thermal conductivity (1.33–1.43 W/(m•K), 26–1000 °C). The comprehensive performance improvement can be attributed to the high-entropy effect, dual-phase nature, and significant differences in ionic radius and atomic mass. This study provides valuable insight into the development of high-entropy RE2Zr2O7 and suggests their significant potential in TBCs.

Thermal properties of high-entropy RE-disilicates controlled by high throughput composition design and optimization

The configuration entropy was manipulated by introducing atoms with unique properties using the high throughput calculations, and five new disilicates with ideal properties which have lower thermal conductivity and controllable thermal expansion coefficient were obtained through composition design. From a microstructural perspective, the inclusion of atoms with larger ionic radius differences (reaching a 4.11 % contrast with Yb2Si2O7) can cause sever lattice shrinkage (9.49 % compared to single-component disilicates), which leads to lower thermal conductivity and a change in the thermal expansion coefficient. At 1200 °C, the thermal expansion coefficient of the five high-entropy disilicates ranged from 4.57 × 10-6 K−1 to 4.84 × 10-6 K−1, and the minimum thermal conductivity was only 1.14 W/m·K. Additionally, the local charge disorder facilitates the transfer of electrons around Si-O to Sc, which reduces the covalent bond strength of Si-O and regulates the thermal expansion coefficient. This phenomenon has been proved in the five non-equimolar high-entropy disilicates with different contents of Sc, effectively regulating the thermal expansion coefficient in 4.08 × 10-6 K−1 to 5.04 × 10-6 K−1. This study presents a novel method for controlling the thermal properties of disilicates and expands the possibilities for selecting thermal protective coating materials for ultra-high temperature SiC-based ceramic composites.