Search Results (258)

Nickel ferrite (NiFe₂O₄) is one of the most studied inverse-spinel ferrites because it combines moderate saturation magnetization, comparatively high electrical resistivity, chemical stability, and broad synthesis flexibility. Yet the literature shows that the measured structure and magnetism of NiFe₂O₄ are not intrinsic constants; they evolve strongly with dimensionality, size, thickness, strain state, cation distribution, surface spin disorder, and synthesis pathway. This review develops a unified theoretical and literature-based interpretation of how dimensionality reshapes the structural and magnetic behavior of NiFe₂O₄ across bulk ceramics, nanoparticles, one-dimensional nanostructures, polycrystalline thin films, and ultrathin epitaxial films. The review is anchored in the two uploaded nickel ferrite attachments and expanded using internet-sourced journal literature on spinel inversion, surface effects, mechanochemical synthesis, sputtered and pulsed laser deposited thin films, and epitaxial ultrathin-film anomalies. The central novelty of this article is the formulation of a dimensionality-dependent framework in which the observed magnetic response is governed by a competition among three coupled factors: (i) the cation-distribution function, which controls the A–B superexchange balance and therefore the net ferrimagnetic moment; (ii) the microstructural coherence function, which measures how crystallinity, strain, defects, and anti-phase boundaries preserve or degrade exchange continuity; and (iii) the surface/interface spin-order parameter, which quantifies the loss or reconfiguration of magnetic order at free surfaces and buried interfaces. Within this framework, bulk NiFe₂O₄ behaves as a near-equilibrium inverse spinel with relatively stable magnetization, whereas nanoscale NiFe₂O₄ experiences strong spin canting and finite-size suppression due to the growing fraction of disordered surface spins. Thin films introduce a distinct regime in which strain, texture, anti-phase boundaries, substrate mismatch, and growth kinetics determine both anisotropy and magnetization. In ultrathin epitaxial films, off-equilibrium cation redistribution and interface-controlled electronic reconstruction may even generate magnetization values far above bulk expectations. The review also compares major synthesis routes—solid-state reaction, sol–gel, co-precipitation, hydrothermal growth, reactive milling, combustion, pulsed laser deposition, and radio-frequency sputtering—and explains why each route biases the final dimensionality-dependent properties differently. A set of word-style equations is provided to formalize spinel inversion, finite-size suppression, anisotropy scaling, coercivity trends, and superparamagnetic crossover. Beyond summarizing the field, the review proposes a regime map linking dimensionality to characteristic structural defects and magnetic signatures, and it identifies unresolved questions concerning the true origin of enhanced magnetization in ultrathin NiFe₂O₄, the interplay between anti-phase boundaries and strain, and the distinction between intrinsic inversion changes and extrinsic substrate artifacts. The resulting article offers a submission-ready, originality-focused review that positions dimensionality as the master variable governing structure–magnetism correlations in nickel ferrite. Full article

The cell envelope of Gram-positive bacteria is a primary target of host immune defenses and antibiotics, and its stability is influenced by environmental factors, including the availability of the divalent cations Mg²⁺ and Ca²⁺. Alanine also plays a critical role in cell envelope integrity, contributing to peptidoglycan cross-linking, D-alanine modification of teichoic acids, and protein synthesis. However, how these factors functionally interact to maintain envelope stability in S. aureus remains unclear. Here, we demonstrate that growth of S. aureus under Mg²⁺-limited and Ca²⁺-limited conditions requires increased alanine uptake mediated by the transporter AapA. Loss of AapA results in increased cell lysis and impaired growth under cation-limited conditions, and removing alanine from the growth medium phenocopies these aapA mutant defects. Alanine limitation increases susceptibility to the detergent Triton X-100 and the membrane-targeting antibiotic daptomycin, consistent with defects in envelope stability. Furthermore, aapA function contributes to bacterial fitness in insect and murine infection models. Together, these findings indicate that Mg²⁺, Ca²⁺, and alanine play overlapping roles in stabilizing the S. aureus cell envelope, pointing to AapA as a target that may leveraged to enhance antimicrobial efficacy. Full article

CeO₂ is a representative oxygen-storage oxide because its fluorite lattice can reversibly release and reincorporate oxygen through the Ce⁴⁺/Ce³⁺ redox couple and the associated formation and annihilation of oxygen vacancies. Although doped CeO₂ has been studied extensively, the literature has often treated oxygen-storage enhancement mainly in terms of dopant identity and composition, whereas the more fundamental issue is how a given doping strategy constructs a specific defect state within the fluorite host. Here, oxygen-storage enhancement is discussed from the standpoint of defect-state engineering. The discussion focuses on three routes, as follows: rare-earth single doping, cation–anion co-doping, and route-dependent dopant incorporation. Rare-earth single doping correlates aliovalent substitution with lattice expansion, vacancy generation, and finite oxygen-storage-capacity (OSC) optima. Cation–anion co-doping further shows that simultaneous perturbation of the cationic and anionic sublattices can amplify the defect response, while also demonstrating that vacancy concentration alone does not fully account for OSC enhancement. Route-dependent doping adds an additional dimension by showing that the same dopant can produce different lattice responses, defect populations, and oxygen-release behaviors when introduced through different pathways. On this basis, the review argues that OSC in doped CeO₂ is more meaningfully rationalized through a coupled descriptor set involving lattice accommodation, Ce³⁺/Ce⁴⁺ redistribution, oxygen-vacancy abundance, and dopant incorporation pathway. Taken together, these observations shift the design logic of oxygen-storage ceria from empirical dopant screening toward deliberate defect-state construction. Full article

The advancement of microelectromechanical systems (MEMS) drives the demand for multifunctional ferroelectrics that synergistically combine substantial strain with competitive energy storage capabilities. In this work, the simultaneous enhancement of electromechanical strain and energy storage properties is achieved in (1−x)(Bi_0.5Na_0.5)_0.94Ba_0.06(Ti_0.98Mn_0.02)O₃-xSrTiO₃ (0 ≤ x ≤ 0.3) ceramics by synergistically employing A-site defect engineering and the nonergodic/ergodic relaxor (NR/ER) phase boundary design. The incorporation of Sr²⁺ plays a dual role: it induces cationic disorder that expands the polarization difference (ΔP = P_max − P_r), thereby effectively boosting the recoverable energy density (W_rec). Concurrently, it stabilizes a critical NR/ER phase ratio near room temperature, which maximizes the strain while minimizing the strain hysteresis. Consequently, when x = 0.15, the optimized system delivers a large strain of 0.45% (d₃₃* = 562 pm/V) with low hysteresis (H = 10.8%). In addition, the x = 0.25 composition exhibits an enhanced W_rec of 1.06 J/cm³, a competitive energy-storage potential (W_rec/E) of 0.013 mC/cm², and a high efficiency (η) of 81% under 80 kV/cm. This work provides an effective strategy for developing multifunctional lead-free materials for integrated actuators and energy storage devices. Full article

The safe immobilization of high-level waste (as actinide) remains a critical bottleneck in the disposal of high-level radioactive waste worldwide. Moreover, the higher specific surface area and surface energy of nano-scale powders enable the production of ceramic materials featuring denser crystal structures and superior strength, hardness, and toughness. Therefore, in this study, Gd³⁺ was used as a surrogate for actinides, and Nb⁵⁺ was introduced as a high-valence charge-compensating cation. Nano-scale powders of CaCO₃, ZrO₂, Gd₂O₃, TiO₂, and Nb₂O₅ were employed to prepare a series of defect-fluorite-derived ceramics, CaZr_1-xGd_xTi_2-xNb_xO₇ (x = 0.1–1.0), via a high-temperature solid-state reaction method, aiming to investigate the atomic substitution mechanisms, phase evolution, and chemical stability under high-valence charge compensation. Laboratory X-ray diffraction (XRD), synchrotron X-ray diffraction (SXRD), and backscattered scanning electron microscopy with energy-dispersive X-ray spectroscopy (BSEM-EDX) confirmed a phase evolution sequence from zirconolite-2M to zirconolite-4M and finally to pyrochlore. This behavior is consistent with that reported for other Ln³⁺-Nb⁵⁺ co-doped zirconolite systems. Rietveld refinement of the SXRD data further revealed, for the first time, the site-occupancy mechanism of Gd and Nb in zirconolite-4M. In both zirconolite-2M and zirconolite-4M, Gd preferentially occupies the Ca sites, whereas Nb substitutes at the Ti sites. In the pyrochlore structure, Ca, Zr, and Gd occupy the 16d sites, while Ti and Nb occupy the 16c sites. Static leaching tests following the MCC-1 protocol showed that pyrochlore exhibits the highest leaching resistance, whereas zirconolite-2M shows the lowest. After 28 days, the highest Gd leaching rate was 1.92(1) × 10⁻⁵ g m⁻² d⁻¹. These results provide new insights into actinide immobilization behavior and compositional design in zirconolite-based waste forms. Full article

Narrow-bandgap tin–lead (Sn–Pb) perovskite solar cells (PSCs) are essential for high-performance tandem photovoltaics, yet their operational stability and efficiency suffer from spontaneous Sn²⁺ oxidation, interfacial defects, and non-radiative recombination. Current passivation strategies often provide only a single modification mode and struggle to adequately stabilize Sn²⁺ without introducing charge-transport barriers. Here, we introduce morpholine acetate (MPAC) as a novel interfacial passivator to achieve synergistic chemical and field-effect passivation in Sn–Pb perovskites. The acetate group of MPAC coordinates with undercoordinated metal cations, suppressing Sn²⁺ oxidation and minimizing defect states. Simultaneously, the morpholine moiety forms an interfacial dipole layer that aligns energy levels to facilitate charge extraction. Consequently, MPAC-modified PSCs achieve a champion power conversion efficiency of 22.64%. Under continuous AM 1.5G illumination without optical filters (xenon lamp, 65 °C, open-circuit conditions), the unencapsulated devices maintain over 90% of their initial efficiency after 192 h, providing a promising route to balance performance and durability. Full article

Yellow and pink calcite samples from the Huanggangliang and Xilingol mining areas in Inner Mongolia were investigated to elucidate the relationships among chemical composition, unit-cell parameters, coloration, and luminescence. Electron probe micro-analysis, laser ablation inductively coupled plasma mass spectrometry, X-ray diffraction, infrared spectroscopy, Raman spectroscopy, UV-Vis absorption spectroscopy, and photoluminescence measurements show that samples of yellow and pink calcite differ significantly in impurity incorporation and optical behavior. Yellow calcite is relatively enriched in Mg and rare earth elements, especially Y and Ce, whereas pink calcite contains markedly higher Mn and Fe contents. The pink calcite has smaller lattice parameters and unit-cell volume, consistent with greater substitution of Ca²⁺ by smaller-radius cations. Spectra reveal that the pink coloration is mainly related to Mn-associated absorption bands at 402 and 527 nm, whereas the yellow color is attributed to weak impurity- and defect-related absorption. Under ultraviolet excitation, yellow calcite exhibits a broad blue–white emission centered at ~470 nm, whereas pink calcite shows an intense orange–red emission near 625 nm characteristic of Mn²⁺. Variable-temperature photoluminescence further demonstrates that the pink calcite has higher thermal stability, with a thermal-quenching activation energy of 0.218 eV, compared with 0.074 eV for the yellow calcite. These results demonstrate that trace element incorporation plays a key role in regulating the coloration and luminescence of calcite and provide useful insight into the optical behavior of carbonate minerals. Full article

Vacancy-ordered double-perovskite Cs₂SnI₆ is known to be a good candidate for perovskite photovoltaics, as it is a light harvesting material which has potential both as an individual compound and as a component of a composite material. The compound is interesting due to being free of atom sites in B cationic positions, making the lattice “breathable” and giving it optoelectronic characteristics that vary with dopants. Here, antimony was examined as a possible heterovalent dopant with an ionic radius larger than that of Sn⁴⁺. In practice, it has been found that most of the materials are composites of Cs₂SnI₆ and Cs₃Sb₂I₉ phases. In the CsI–SnI₄–SbI₃ phase triangle, the melt crystallization process produced a layered (111)-oriented microstructure of crystallites with an increasing percentage of antimony. Two-dimensional perovskite materials look more promising in the decomposition of a solid solution to Cs₂SnI₆ and Cs₃Sb₂I₉ phases than in heterophase nucleation. The observed effect of (111)-oriented growth could be translated to other inorganic halides to form new oriented films or single crystals of perovskite materials. Diffuse reflectance spectroscopy showed an additional absorption shoulder in the NIR region for all groups of compounds, most likely induced by point defects in I sublattices of Cs₂SnI₆. Expanding the Cs₂SnI₆ absorption range to the NIR region could lead to new perspectives for its application. Full article

Properties of composite materials with polymer matrix and inorganic filler are affected by preparation methods and starting components’ properties. For example, filler powder particle size distribution, phase composition and presence/absence of dopants can greatly affect properties of resulting composites. The present research attempts to clarify the influence of synthetic CaCO₃ powder properties on alginate/CaCO₃ composite material preparation process. Composite materials in the form of granules, networks and films were created from suspensions of synthetic powders of calcium carbonates CaCO₃ in aqueous solutions of sodium alginate. Powders of calcium carbonates CaCO₃ were synthesized from 0.5 M aqueous solutions of calcium chloride CaCl₂ and aqueous solutions of potassium K₂CO₃ (at molar ratio Ca/CO₃ = 1), sodium Na₂CO₃ (at molar ratio Ca/CO₃ = 1), and ammonium (NH₄)₂CO₃ (at molar ratios Ca/CO₃ = 1 and Ca/CO₃ = 0.5) carbonates. Phase composition of powder synthesized from CaCl₂ and K₂CO₃ was presented by calcite. Phase composition of powders synthesized from other soluble carbonates included calcite and vaterite. The powder preparation protocol excluded the stage of synthesized powder washing for by-product removal. This preparation protocol provided preservation of reaction by-product in the synthesized powder at a very low level. The presence of NH₄Cl as a reaction by-product even in small quantities can be taken as a reason for visually observed subsequences of cross-linking reaction at the stage of suspensions preparation. Aqueous solution of sodium alginate and suspensions containing powders synthesized from potassium K₂CO₃ and sodium Na₂CO₃ carbonates demonstrated similar dependence of viscosities from shear rate. The presence of (NH₄)₂CO₃ in the powder synthesized at molar ratio Ca/CO₃ = 0.5 was the reason for the lower viscosity of the suspension in comparison with suspensions loaded with powders containing KCl, NaCl and (NH₄)₂Cl as reaction by-products due to decomposition of unstable (NH₄)₂CO₃ and gas phase formation. The presence of (NH₄)₂Cl in the powder synthesized at molar ratio Ca/CO₃ = 1 in contrast was a reason for the highest viscosity suspension in comparison with those under investigation. Additionally, (NH₄)₂Cl presence in synthetic powders shows the ability to facilitate partial dissolution of CaCO₃ providing a higher concentration of Ca²⁺ cations at the stage of suspension preparation, thus aiding the cross-linking process of alginate hydrogel. Granules, meshes and films were created via interaction of suspensions of calcium carbonates CaCO₃ in aqueous solutions of sodium alginate with 0.25 M aqueous solutions of calcium chloride CaCl₂ to provide the formation of matrix of composites via Ca-crosslinking of sodium alginate followed by washing and freeze drying under deep vacuum. The created composite materials in the form of granules, meshes and films based on Ca-cross-linked alginate and powders of synthetic calcium carbonate can be recommended for skin wound and bone defect treatment and drug delivery carriers. Full article

This study investigates how torch standoff distance influences the microstructure, surface topography, and progressive-load scratch response of air plasma-sprayed 8YSZ and rare-earth co-doped GdYbYSZ thermal barrier coatings on an St-52 grade carbon steel substrate. Three nozzle-to-substrate spraying distances were examined: 80, 100, and 120 mm. X-ray diffraction revealed that the 8YSZ coatings possessed a predominantly tetragonal (t′) structure, with minor monoclinic fractions detected in the coatings obtained with the 80 mm and 100 mm distance parameters. The GdYbYSZ coatings, in contrast, exhibited a single-phase cubic defect-fluorite structure; their diffraction peaks appeared at lower 2θ angles relative to undoped cubic ZrO₂, consistent with lattice expansion caused by the substitution of Zr⁴⁺ by the larger Gd³⁺ and Yb³⁺ cations. Surface topography was quantified by non-contact laser profilometry, providing areal (Sa) and profile (Ra) roughness parameters for the as-sprayed condition as well as three-dimensional scratch-damage morphology after testing. Progressive-load scratch tests were performed using a Rockwell diamond indenter over a 2 mm track with the normal load ramped from 0.03 N to 30 N. Penetration depth, residual depth, tangential force, and acoustic emission were recorded continuously to identify critical damage transitions. Across all spraying distances, 8YSZ exhibited systematically shallower scratch grooves than GdYbYSZ; end-of-track maximum groove depths remained below 37 µm for 8YSZ, whereas GdYbYSZ reached up to 72 µm under identical loading conditions. The novelty of this study lies in combining torch standoff distance as a processing variable with multi-channel progressive-load scratch diagnostics, including in situ acoustic emission, depth profiling, and friction monitoring, to comparatively assess the scratch wear performance of 8YSZ and rare-earth co-doped zirconia TBCs for the first time. Full article

The oxygen evolution reaction (OER) is the rate-limiting step in alkaline water electrolysis for hydrogen production. Owing to their earth abundance and high intrinsic activity, transition metal-based catalysts (TMBCs) have emerged as promising alternatives to noble-metal catalysts, with defect engineering recognized as an effective strategy for enhancing OER performance. This review systematically summarizes recent advances in regulating alkaline OER activity of TMBCs through vacancy defects, including anion vacancies, cation vacancies, and divacancies. First, the alkaline OER mechanism, key performance evaluation parameters, and activity descriptors are briefly introduced. The formation mechanisms and regulation strategies of different vacancy types are discussed, with emphasis on how vacancy defects enhance OER performance by modulating electronic structures, optimizing active sites, and tuning adsorption–desorption behaviors of reaction intermediates. In addition, the advantages and application scenarios of various characterization techniques for vacancy defects are summarized. Finally, current challenges are identified, and future research directions are proposed. This review provides theoretical and practical references for the rational design of high-performance transition metal-based OER catalysts and the large-scale advancement of alkaline water electrolysis for hydrogen production. Full article

Heavily doped metal oxide thin films combining high visible transmittance and low electrical resistance are used in a multitude of optoelectronic devices, where their performance is highly dependent on the structural defects and density of electronic states associated with doping. This study explores the structural, optical, and electronic properties of Sn-doped indium oxide (In₂O₃:Sn) and Al-doped zinc oxide (ZnO:Al) thin films, which were prepared by sputtering on unheated glass substrates and subsequently annealed in N₂ at different temperatures between 250 °C and 450 °C. These samples reach free electron densities above 10²⁰ cm⁻³ due to the presence of extrinsic donors (mainly substitutional defects of Sn_In and Al_Zn) and also intrinsic donors (oxygen vacancies), which change with the annealing temperature due to oxygen desorption and/or cation migration processes. The volume of the crystal lattice expands (up to a maximum of 1.1%) and the band gap widens (up to a maximum of 17.9%) with respect to the undoped material, increasing with electron density. Additional absorption is due to band tail, at an energy ~10% below the undoped band gap, which varies slightly with the carrier concentration. The same general behavior is observed for both materials, with particularities in terms of crystal lattice and electronic states, which can be tuned by the heating temperature. Full article

High-entropy fluorite oxides offer exceptional tunability of structure and functionality through controlled multi-cation substitution. In this work, Ce-Zr-Pr-Sm-Eu-based high-entropy oxides, with systematically varied Pr content, were synthesized using a modified sol–gel citrate method to investigate the influence of Pr incorporation on lattice structure, defect formation, and photocatalytic performance. All compositions crystallized in a single-phase cubic fluorite structure, where increasing Pr concentration induced gradual lattice expansion and microstrain due to the substitution of larger Pr³⁺ ions. Morphological and surface analyses revealed porous nanostructures at moderate Pr levels, while excessive Pr promoted densification and reduced surface accessibility. Spectroscopic studies confirmed the coexistence of Pr³⁺/Pr⁴⁺ and Ce³⁺/Ce⁴⁺ redox couples, strong 4f–2p orbital hybridization, and enhanced defect-related electronic states that narrowed the optical bandgap. The optimized Pr-doped composition exhibited almost 100% degradation of methylene blue under UV light over 30 min, untypical for semiconductors with a narrower bandgap, and is enabled by efficient charge separation and redox cycling between Ce and Pr centers. Full article

The pursuit of sustainable ammonia production has accelerated the development of electrocatalytic pathways capable of operating under ambient conditions with renewable electricity. Recent studies have revealed that the efficiency and selectivity of both electrochemical nitrogen reduction reaction (eNRR) and nitrate reduction reaction (eNO₃RR) are not governed solely by catalyst composition, but by the synergistic interplay among electrolyte identity, interfacial solvation structure, and catalyst architecture. Hydrated cations such as Li⁺ profoundly reshape the electric double layer, polarize interfacial water, and lower activation barriers for key proton–electron transfer steps, thereby redefining the electrolyte as an active promoter. Parallel advances in structural engineering, including alloying, heteroatom doping, controlled defect formation, and nanoscale morphological control, have enabled the optimization of intermediate adsorption energies while simultaneously suppressing competing hydrogen evolution. In addition, the emergence of metal–organic-framework (MOF)-derived single-atom catalysts has demonstrated that atomically dispersed transition-metal centers anchored within dynamically adaptable matrices can deliver exceptional Faradaic efficiencies, high turnover rates, and long-term operational durability. These developments highlight a unified strategy in which electrolyte–catalyst coupling, rational structural modification, and atomic-scale design principles converge to enable predictable and high-performance ammonia electrosynthesis. This review integrates mechanistic insights across these domains and outlines future directions for translating molecular-level understanding into scalable technologies for green ammonia production. Full article

Rapid removal of chemically diverse organic pollutants remains a major challenge in aqueous decontamination. In this study, atmosphere-controlled defect engineering was used to activate anatase TiO₂ as a rapid adsorbent operating on the minute scale, exhibiting low charge selectivity under the investigated conditions. A reduced black TiO₂ (B–TiO₂), produced by inert annealing, achieved ≈100% removal of cationic methylene blue within ~6 min and ≈91% uptake of anionic methyl orange within ~3 min, whereas pristine and air-annealed TiO₂ showed only marginal adsorption under identical conditions. Correlative structural and surface-sensitive analyses indicated that this behaviour was associated with a chemically activated near-surface region enriched in reduced titanium contributions, defect-associated or non-lattice oxygen environments and a locally perturbed anatase framework, together with finely dispersed carbon-related motifs integrated within the oxide matrix. Adsorption kinetics were described, within experimental resolution, by pseudo-second-order fitting, while intraparticle diffusion analysis supported sequential regimes initiated by rapid interfacial attachment. Equilibrium analysis yielded apparent maximum capacities of 6.116 mg g⁻¹ for methylene blue and 2.950 mg g⁻¹ for methyl orange, reflecting adsorption governed by surface heterogeneity for cationic species and an apparent saturation-type response for anionic uptake. Overall, controlled surface non-stoichiometry emerges as a viable strategy to enhance adsorption kinetics in TiO₂, providing a transferable design framework for developing oxide-based adsorbents for sustainable water-treatment applications. Full article