Cation Radius Research Articles

Insight into the Rate-Determining Step in Photocatalytic Z-Scheme Overall Water Splitting by Employing A Series of Perovskite RTaON2 (R = Pr, Nd, Sm, and Gd) as Model Photocatalysts.

Photocatalysis is an intricate process that involves a multitude of physical and chemical factors operating across diverse temporal and spatial scales. Identifying the dominant factors that influence photocatalyst performance is one of the central challenges in the field. Here, we synthesized a series of perovskite RTaON2 semiconductors with different A-site rare earth atoms (R = Pr, Nd, Sm, and Gd) as model photocatalysts to discuss the influence of the A-site modulation on their local structures as well as both physical and chemical properties and to get insight into the rate-determining step in photocatalytic Z-scheme overall water splitting (OWS). It is interesting to find that, with a decreasing ionic radius of the A-site cations, the RTaON2 compounds exhibit continuous blue shift of light absorption and a concomitant reduction in the lifetime of photogenerated carriers, revealing a significant influence of A-site atoms on the light absorption and charge separation processes. On the other hand, the A-site atomic substitution was revealed to significantly modulate the valence band positions as well as surface oxidation kinetics. By employing the Pt-modified RTaON2 as H2-evolving photocatalysts, the activity of photocatalytic Z-scheme OWS for hydrogen production on them is found to be determined by its surface oxidation process instead of light absorption or charge separation. Our results give the first experimental demonstration of the rate-determining step during the photocatalytic Z-scheme OWS processes, as should be instructive for the design and development of other efficient solar-to-chemical energy conversion systems.

Mitigating anodic corrosion in aluminum–air batteries: Effects of alkali metal cation size on electrochemical performance

Anodic corrosion limits the performance of aluminum–air batteries (AABs) by reducing discharge capacity and hindering energy density. This study proposes a strategy to mitigate anodic corrosion by controlling electrolyte cations to decrease the activity of free water molecules in the anodic corrosion process. Alkali metal cations (Na+, K+, Rb+) are introduced into a 1mol dm−3 KOH solution to examine their solvation properties and effects on free water molecule activity. Results show that larger cations (Na+ < K+ < Rb+) enhance anode discharge capacity by promoting more stable discharge reactions. Raman spectroscopy reveals that as cation radius increases, free water molecule activity decreases due to increased hydration. X-ray photoelectron spectroscopy analysis shows that larger cations favor the formation of corrosion-resistant aluminum compounds like Al2O3 and Al(OH)3, due to their higher concentration in the electric double layer, inhibiting anodic corrosion. This study highlights the critical role of cation solvation in enhancing electrochemical performance and corrosion resistance of AAB anodes.

Electrochemical aspects of Li[Ni0.6Co0.2Mn0.2]O2 cathode materials doped by various ionic radius cations

The capacity of Li[Ni0.6Co0.2Mn0.2]O2 cathode materials decreases rapidly due to layer structure degradation, grain cracking, and electrolyte side reaction during cycling. In this paper, metal ions with different ionic radius (W6+= 0.62 Å, Mg2+= 0.72 Å, Y3+= 0.90 Å) were doped into single crystal Li[Ni0.6Co0.2Mn0.2]O2, which were synthesized by high-temperature solid-phase technology. X-ray diffraction (XRD), energy dispersive spectrometry (EDS) and scanning electron microscopy (SEM) were employed to characterize various samples doped with different ionic radius. The results reveal that the radius of the doped ions plays a crucial role in improving the stability of material structure. It is attributed to the incorporation of metal ions into the Li+ or Ni2+ site, thus maintaining the integrity of the layer and reducing cation mixing. However, it is also detrimental to the performance of single crystal Li[Ni0.6Co0.2Mn0.2]O2 because of lattice distortion caused by the ionic radius of the doped metal being much greater than that of the doped site. These results show superior capability and reveal the performance trend of Li[Ni0.6Co0.2Mn0.2]O2 with metal ions of different radius. The initial discharge capacity at 0.1 C for the undoped sample was 183.8 mAh/g, compared with 189.9, 192.3 and 199.8 mAh/g for NCM622-W, NCM622-Mg, and NCM622-Y, respectively. After 100 cycles, NCM, NCM-W, NCM-Mg, and NCM-Y delivered retentions of 90.88 %, 98.16 %, 97.13 %, 94.37 %, respectively. The defect model is mainly responsible for the improvement in electrochemical performance.

Thermally activated damage recovery in ion‐irradiated Gd2Ti2‐yZryO7 pyrochlore

AbstractIonizing events having a wide variety of radiation‐induced effects can radically affect the kinetics of defect production or structural transformation in the pyrochlore structured oxides (A2B2O7). Therefore, a thorough understanding of the kinetics associated with cation ordering and disordering is required for various technological applications. The structural responses of Gd2Ti2‐yZryO7 (y = 0.4, 1.2, 1.6) pyrochlore series irradiated by 120 MeV Au9+ ions were investigated using in situ synchrotron x‐ray diffraction (SR‐XRD), micro‐Raman spectroscopy, and scanning electron microscopy (SEM). Each pyrochlore composition irradiated at the highest fluence, where structural modifications occur, was subsequently isochronally annealed from room temperature to 1000°C. The SR‐XRD results indicate that Ti‐rich composition (y = 0.4) retains its pre‐irradiated pyrochlore structure (Fdm) at 1000°C. In contrast, Zr‐rich compositions exhibit recrystallization to an intermediate defect‐fluorite phase (Fmm) above 500°C, and the pre‐irradiated pyrochlore superstructure does not recover even on annealing at 1000°C. These results reveal that recrystallization temperature strongly depends on the accumulated radiation damage, generally described with the cationic radius ratio (rA/rB). Thus, investigation of the thermal annealing behavior of irradiated pyrochlores helps better understanding the general mechanisms of radiation damage and recovery of pyrochlores, which is important for their use in nuclear applications.

Study on the role of alkali halides on the mutarotation and dehydration of d-xylose in aqueous solution

Although the xylose mutarotation and transformation have been investigated largely separately, their relationship has been rarely systematically elaborated. The effect of several factors such as xylose concentration, temperature, and salt concentration, affecting the mutarotation of xylose are discussed. Nine alkali halides (LiCl, NaCl, KCl, LiBr, NaBr, KBr, LiI, NaI, and KI) are used to test salt effects. The relationship between xylose rotation rate constant (kM), specific optical rotation at equilibrium ([α]eqm), α/β ratio, H chemical shift difference (ΔΔδ), Gibbs free energy difference (ΔG), hydrogen ion or hydroxide ion concentration ([H+] or [OH−]), and xylose conversion is discussed. Different salts dissolved in water result in different pH of the solutions, which affect the mutarotation of xylose, with the nature of both cation and anion. Shortly, the smaller the cation radius is and the larger the anion radius is, the greater the mutarotation rate is. In the dehydration of xylose to furfural in salty solutions, xylose conversion is positively correlated to mutarotation rate, H+ or OH− concentration, and the energy difference between α-xylopyranose and β-xylopyranose. Although the [α]eqm of xylose is positively correlated with α/β configuration ratio, there is no obvious correlation with xylose dehydration. The conversion to furfural in chlorides is superior to that in bromines and iodides, which is due to the fact that the pH of chloride salts is smaller than that of the corresponding bromide and iodized salts. Higher H+ concentration prefers to accelerate the formation of furfural. In basic salt solutions, the xylulose selectivity is higher than that of furfural at the initial stage of reaction. The furfural selectivity and carbon balance are better in acidic condition rather than in basic condition. In H2O-MTHF (2-Methyltetrahydrofuran) biphasic system, the optimal furfural selectivity of 81.0 % is achieved at 190 °C in 1 h with the assistance of LiI and a little HCl (0.2 mmol, 8 mmol/L in aqueous phase). A high mutarotation rate represents rapid xylose conversion, but a high furfural selectivity prefers in acidic solutions, which would be perfect if organic solvents were available to form biphasic systems.

Ternary cesium(rubidium) tungstates: production and impedance spectroscopy

The work is aimed at the directed synthesis of new phases of tungstates containing mono-, tri-, and tetravalent metals, as well as the determination of their crystallographic, thermal, and electrophysical properties. The study used the method of solid-phase synthesis to obtain tungstate phases with composition MRA0.5(WO4)3 (M – singly, R – triply-, and A – tetra-charged elements) within the temperature range of 400–750 °С. Their crystallographic and thermal characteristics were determined. The synthesized ternary tungstates crystallizing in a hexagonal system were studied using differential scanning calorimetry. The technique revealed an increase in the melting temperatures of compounds with increasing ionic radius of the trivalent cation in the series CsRTi0.5(WO4)3 (R = Al, Cr, Ga, Fe, In). The same correlation is observed when switching from rubidium to cesium derivatives. The thermal stability of ternary titanium and hafnium tungstates was compared. The melting temperatures of RbRTi0.5(WO4)3 are about 20 °С higher than those of their hafnium counterparts. The dielectric characteristics of CsRTi0.5(WO4)3 (R = Fe, Cr) belonging to the ternary tungstate family were analyzed via impedance spectroscopy. The temperature and frequency dependences of the conductivity of ternary tungstates at different frequencies (1 Hz – 1 mHz), measured in heating and cooling modes, are characterized by a slight temperature hysteresis, reaching 10-2–10-3 S/cm in the high-temperature region at activation energy values of 0.4–0.5 eV. The impedance frequency spectra measured within the range of 1 Hz – 1 mHz at different temperatures confirm the ion-conducting properties of the sample, which allows the obtained phases to be considered promising solid electrolytes.

Elucidation of structural, electromagnetic, and optical properties of Cu–Mg ferrite nanoparticles

Copper doped magnesium ferrite, Mg1-xCuxFe2O4(x = 0.0–1.0) nanomaterials were synthesized via. sol-gel method sintered at 600 °C for 2 h. The synthesized materials were characterized using modern sophisticated techniques viz. X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy, Energy dispersive x-ray spectroscopy (EDS), Vibrating sample magnetometer, UV–visible diffuse reflectance spectra and Impedance analyzer. XRD analysis revealed that all the samples were single phase cubic spinel structure with Fd3m space group and investigated the change in structural parameters with copper concentration. The average crystallite size in the range of 11–23 nm and lattice parameters decrease with increasing Cu doping, due to the cationic distribution and ionic radius. The SEM images show the agglomeration of the particles with spherical like shape and elemental percentage were obtained from EDX. The saturation magnetization showed an increasing trend with increasing Cu concentration at a certain level and then decreases due to the rearrangement of cations at tetrahedral and octahedral sites. The Coercivity, Retentivity and magnetic crystalline anisotropy increase with changing dopant concentration. The magnetic measurements showed enhanced saturation magnetization at certain level (28.96emu/gm) and increase in coercivity up to 1102 Oe with changing dopant concentration. The estimated band gap energy is found to increase with Cu content. The dielectric constant, dielectric loss and impedance show normal behavior of ferrite. The frequency dependent dielectric constant decrease and tan delta shows a relaxation behavior at low frequencies. The synthesized nano Mg–Cu nanoparticles will be applied as humidity sensor, gas sensor, microwave devices and photocatalyst.

Investigation of structural and optoelectronic integrity of Sm3+ doped CaWO4 for LED applications

In this study we illustrate the structural, electronic and optical integrity of Ca1-xSm(2/3)xWO4 (x = 0.00, 0.02, 0.04, 0.06 and 0.08) crystals for optoelectronic applications via experimental and first principles approach. According to our experimental outcomes, CaWO4 crystallizes in scheelite type tetragonal structure devoid of impurity which depends on the A-site cationic radius and dopant-host compatibility. As a result, the dopant induced lattice distortion occur due to symmetric and asymmetric stretching of (Ca, Sm)—O and W–O bonds within [CaO8] and [WO4] cluster. According to our FT-IR and Raman spectral analysis, the non-centrosymmetric vibration within the [WO4]2- complex gives rise to internal modes while the Ca2+/Sm3+ cationic displacement and rigid molecular ionic group constitutes the external modes which equally impacts the electronic and optical characteristics of the host material. While the forbidden gap extends due to Sm3+ substitution, the delocalization of W-5d orbitals on the other hand occur due to rising distortions within the WO4 cluster. As a result, the polarization between [WO4] and [CaO8] cluster and difference in the electronic transitions controls the optical characteristics of the host material. According to our experimental and theoretical predictions, a noticeable decrease in the optical band gap (5.96–5.83 eV) occurs due to heterovalent cationic substitution (Sm3+), difference in structural order-disorder and charge carrier density. As a result, a broad photoluminescence (PL) spectrum among acceptor doped samples verifies the impact of multi-phonon or multi-level processes on the luminosity of the host material.

Cation doping for enhanced layer spacing and electrochemical performance in Li-rich Mn-based lithium-ion cathode materials

Lithium-rich manganese-based cathode materials offer promising research avenues owing to their high capacity. This study delved into the impact of cation doping on Li1.2Ni0.13Co0.13Mn0.54O2(LNCMO). A range of layered Li1.2BXNi0.13Co0.13Mn0.54O2 (LNCMOxB, B = Ca, Na, Al) cathode materials were produced utilizing calcium, sodium, and aluminum chloride as dopants. Combining these elements with the lithium-rich materials improves the capacity retention of the positive electrode and mitigates voltage decay. X-ray diffraction analysis, Rietveld structural refinement, SEM, and XPS verified the inclusion of Ca, Na, and Al in the synthesized samples. Electrochemical analysis revealed that the LNCMO-0.01Na sample, possessing the largest dopant radius, exhibited favorable cyclic stability at 0.2C. Conversely, the LNCMO-0.01Al sample, featuring the smallest doped cation radius, demonstrated superior rate performance. Specifically, after 30 cycles at varying rates, the capacity reached 170 mAh·g−1 at 0.2C. The LNCMO-0.007Ca sample exhibited the highest residual capacity, maintaining 151.4 mAh·g−1 after 100 cycles at 0.2C. Doping Li sites in Li1.2Ni0.13Co0.13Mn0.54O2 materials with appropriately sized divalent cations significantly enhances their overall electrochemical performance. This enhancement is attributed to ion doping within the Li and TM layers, expediting the diffusion kinetics of Li ions, and augmenting ion and electronic conductivity. Investigating the doping modification of lithium-rich manganese-based oxide microspheres is instrumental in advancing positive electrode materials for lithium-ion batteries, aiming for increased specific capacity and more stable material structures.

Revisit the classical theories of the conductance of unassociated electrolytes. Is there reality in relaxation?

The experimental results of the ionic conductance of the electrolytic solution can be explained without the use of relaxation until almost 2M concentration of the NaCl solution within 97% agreement with two parameters: the hydrated ion radii for cations and anions. No other fitting parameters were introduced, and no ion association was assumed. The theory is based on a newly introduced electrochemical potential that incorporates the interaction between ions and fluctuations in electrolyte concentration in the nanosized region. It was found that the concept of local chemical potential, fluctuation in the nanosized area, and symmetry of the system are closely related to the Boltzmann distribution of ions. Extending the concept of a local chemical potential to the case of an external field, the derived ionic mobility automatically includes the effect of electrophoresis. The so-called electrophoretic retardation was found to be equivalent to the shielding effect of the external field. Relaxation bears a minor effect and may contribute to the ion transport of electrolytic solution at most 3%, if exists.

Electronic bonding transitions in oxide glass above two megabar pressures

Inelastic x-ray scattering (IXS) of B2O3 glass up to ∼2.2 Mbar reveals electronic bonding transitions in oxide glasses. B -edge IXS identifies the high-energy feature above ∼1.4 Mbar and a gradual increase in its intensity toward ∼2.2 Mbar, indicating the formation of hypervalent boron via electron polarization to oxygen atoms. The pressure-driven high energy shifts in O -edge IXS indicate pronounced electronic dispersion that increases upon densification of amorphous oxides above ∼2 Mbar. The extent of the energy shifts and enhanced polarization correlate with increasing atomic radius of cation in oxide glass, establishing the role of cation radius in electronic structures of amorphous oxides under compression. The results elucidate the electronic mechanisms behind the structural transformation in low- oxide glasses, where transitions to highly coordinated cations are hindered well above 1 Mbar, providing the origin of incompressibility of low- amorphous oxide under multi-Mbar compression. Published by the American Physical Society 2024

Entangling imidazolium-based ionic liquids and melanins: A crossover study on chemical vs electronic properties and carrier transport mechanisms

Melanins (mel) are a class of pigments that are nearly ubiquitous and among the oldest compounds found in nature. However, their practical application has been limited due to their low solubility in water and in most organic solvents. Recent research on polydopamine has revealed that ionic liquids (ILs) not only enhance melanin’s dissolution but also fine-tune its redox properties through specific dipolar interactions. In this study, we expand upon previous investigations by customizing new suspensions on a broader range of melanins. Concerning ILs, we focus on imidazolium based ILs, tailoring their chemical properties (pKa) and structural characteristics (cation radius, anion radius).The melanins under consideration include synthetic polymers derived from the oxidative polymerization of 5,6-dihydroxyindole (DHI) and its 2-carboxylic acid counterpart (DHICA), as well as the natural pigment Sepiomelanin (Sepiomel), which is isolated from the ink sack of cuttlefish. Our comparative analysis between neat ILs and ILs-mel responses reveals several key findings: the increase in solubility, the tuning of the redox ability, the decrease of the ionic charge resistance (from MΩ τo kΩ); the partial removal of the electrical polarization effects and the delocalized ionic charge hopping mechanisms in conductivity; the increase of the free ionic diffusion mobility and Debye lengths. Notably, electrical transport is influenced by both the chemical features and the steric hindrance in the ILs as well as the specific type of melanin employed. These factors contribute to the high order correlation between free ionic charge densities and their corresponding Debye lengths. Consequently, our findings suggest that for these complex systems, an improved model extending beyond a simplified electrostatic interaction mechanism is required.

Advanced ceramics with integrated structures and functions: Machine learning prediction and experimental verification

Improving the thermal conductivities and bending strengths of ceramic substrates is crucial for their applicability as key components of integrated chips. Herein, we report the latest study in which the thermal conductivity and bending strength of aluminum nitride (AlN) ceramics were systematically predicted using high-precision prediction model approached with a machine learning (ML) method based on extreme gradient enhancement method (XGBoost). The ML model was used to rank the effects of the process parameters, and SHapley Additive exPlanations (SHAP) was employed to quantify the contributions of different factors. Sintering additives were found to have the predominant influence on the thermal conductivity and bending strength; particularly, those with cationic radii within 0.085–0.105 nm enhance both properties. By using Pr2O3 as the sintering additive and adopting the preparation conditions recommended by the ML model, we prepared AlN ceramics with thermal conductivity as high as 195.63 W m−1 K−1 and bending strength of 371.60 ± 9.31 MPa, thus satisfying the application requirement of high thermal conductivity. The proposed model is also applicable to alumina and silicon nitride ceramics. This study provides a practicable and once-for-all strategy to realize the entire process from the ML prediction design to the preparation of ceramic materials exhibiting superior thermal conductivity and high strength.

Eu2+ doping and Mg2+-coupled Zn2+, Ca2+ and Sr2+ cations induce tunable orange-blue luminescence in cordierite

A series of Mg2Al4Si5O18:xEu2+ (x = 0.2, 0.6, 1.4, 2.8, 6.0mol‰) and Mg2Al4Si5O18:0.05B, 1.4Eu2+ (BZn2+, Ca2+ and Sr2+) phosphors were prepared by high-temperature melt ice-water quenching and heat treatment. In this study, using Eu2+ ions as a structural probe, we investigated the effects of heat treatment temperature, Eu2+ ion concentration, and cation position on the crystal phase and local structure, triggering changes in the luminescent properties of the phosphor and achieving coordinated blue and red luminescence. Through heat treatment analysis, we proposed the formation process of the two phases of cordierite. The doping of different concentrations of Eu ions in cordierite triggers the phase transition of the host lattice. The molar distribution ratio of Eu2+ ions was calculated by Gaussian peak-splitting fitting to identify the detailed occupancy distribution of the Eu2+ ions in μ-cordierite and α-cordierite. In the α-cordierite phase, with the doping of Zn2+, Ca2+, and Sr2+ cationic sites, the PL is modulated from orange to blue emission based on the selective occupancy of Eu2+ ions, which is caused by the difference in cationic radii and structural distortion. The comprehensive luminescence intensity of MASE1.4, MASZ0.05E1.4, MASC0.05E1.4, and MASS0.05E1.4 phosphors were 81.18%, 83.49%, 62.67%, and 76.41% at 150 °C compared to that at 30 °C, indicating the better thermal stability of the prepared phosphors. The luminescence tunable strategy by cation and Eu2+ doping simultaneously modifies the emission and achieves different thermal stability, providing a new design concept for the development of Eu2+-doped silicate phosphors.

High-pressure/high-temperature synthesis of a new polymorphic series of lanthanoid cadmium borates, LnCdB6O10(OH)3 (Ln = Sm–Er)

Abstract We report on the synthesis, structure determination, and characterization of a new series of compounds LnCdB6O10(OH)3 (Ln = Sm–Er). Syntheses were carried out in a Walker-type multianvil device at 7 GPa and 650 °C. Structure determinations revealed the coexistence of an orthorhombic and a monoclinic polymorph, depending on the ionic radius of the lanthanoid cation. The orthorhombic structural variants crystallize non-centrosymmetrically in the space group Pna21 (no. 33), while the monoclinic modifications crystallize in space group P21/c (no. 14). Both modifications display a layered crystal structure built up by a repeating [B6O13]8− building block as their main structural feature.

Cation-mediated acid-base pairs for mild oxidative cleavage of lignocellulosic β-1,4-glycosidic bonds

Solar-driven lignocellulosic biomass photoreforming holds significant promise for the production of value-added chemicals and fuels. The cleavage of the β-1,4-glycosidic bond is crucial for the effective conversion of lignocellulosic biomass. Polymeric carbon nitride (PCN) with acid-base pairs (M-C sites) is developed through heteroatomic carbon incorporation and cation insertion. It can be used for the gentle oxidation of cellobiose to monosaccharides, bypassing the formation of organic acids such as gluconic acid and glucaric acid. A series of different alkaline/alkaline-earth cation for regulation of acid-base pairs exhibited a negative correlation between β-1,4-glycosidic bond cleavage and cation radii. In particular, the introduction of short-radius cations (such as Li) into PCN enabled the formation of acid-base (M-C) pairs characterized by strong acidity. It also enhanced electron delocalization around M-C sites, potentially promoting the generation of reactive radicals in the reaction. Electron paramagnetic resonance analysis confirmed the presence of •OH radicals. The mild oxidative species, are the primary reactive radicals responsible for β-1,4-glycosidic bond cleavage in cellobiose. This study provides insightful evidence for the rational regulation of acid-base sites in facilitating β-1,4-glycosidic bond cleavage. It sheds light on the oxidative cleavage mechanisms integral to lignocellulosic biomass photoreforming, offering insights for advancing sustainable biomass conversion technologies.

Yb0.5Ca0.75Si7.5Al4.5O1.5N14.5 α-SiAlON ceramics: A hard material with low thermal conductivity

High hardness is desirable for thermal insulation materials in various applications to improve wear resistance. However, hard materials like diamond, Si3N4, and SiC are often accompanied by high thermal conductivity, due to their strong covalent bonds and high Young’s modulus, which increase sound velocity and benefit heat transportation. How to achieve concurrent high hardness and low thermal conductivity remains a challenge in thermal insulation materials. In this work, we report (Yb+Ca) co-doped α-SiAlON (Yb0.5Ca0.75Si7.5Al4.5O1.5N14.5, a solid solution of α-Si3N4) with a low thermal conductivity of 3.4 W/(m·K) and a hardness of 18.1 GPa at 25℃. The thermal conductivity of α-SiAlONs co-doped by (Yb+Nd/Lu) were also studied, and we found that phonon scattering could be significantly increased only when there was a remarkable difference in cation mass and radius between the co-doping cations, like that between Yb3+ and Ca2+. Additionally, high-entropy α-SiAlONs co-doped by five kinds of cations were studied (e.g., Nd0.1Gd0.1Dy0.1Er0.1Yb0.1Si9.5Al2.5ON15), and we found that the high-entropy strategy is not so effective in pursuing low thermal conductivity in α-SiAlONs. The contribution of different phonon scattering mechanisms in the α-SiAlONs was discussed based on inverse thermal diffusivity. Compared with most other ceramics (e.g., 8YSZ and rare-metal zirconates) with low thermal conductivity, (Yb+Ca) co-doped α-SiAlON has a lower bulk density, higher hardness, and higher toughness, which makes it a potential candidate material for applications requiring both thermal insulation and good mechanical properties.

Novel yellowish-green single-phased spinel Mg1-xBaxAl2O4:Mn2+ phosphor(s) for color rendering white-light-emitting diodes.

For white light-rendering research activities, interpretation by using colored emitting materials is an alternative approach. But there are issues in designing the white color emitting materials. Particularly, differences in thermal and decay properties of discrete red, green, and blue emitting materials led to the quest for the search of a single-phased material, able to emit primary colors for white light generation. The current study is an effort to design a simple, single-phase, and cost-effective material with the tunable emission of primary colors by a series of Mg1-xBaxAl2O4:Mn2+ nanopowders. Doping of manganese ion (Mn2+) in the presence of the larger barium cation (Ba2+) at tetrahedral-sites of the spinel magnesium aluminate (MgAl2O4) structure led to the creation of antisite defects. Doped samples were found to have lower bandgaps compared with MgAl2O4, and hybridization of 3d-orbitals of Mn2+ with O(2p), Mg(2s)/Al(2s3p) was found to be responsible for narrowing the bandgap. The distribution of cations at various sites at random results in a variety of electronic transitions between the valance band and oxygen vacancies as well as electron traps produced the antisite defects. The suggested compositions might be used in white light applications since they have three emission bands with centers at 516 nm (green), 464 nm (blue) and 622 nm (red) at an excitation wavelength of 380 nm. A detailed discussion to analyze the effects of the larger cationic radius of Ba2+ on the lattice strain, unit cell parameters, and cell volumes using X-ray diffraction analysis is presented.

Heavy-ion irradiation effects of high-entropy A2Ti2O7 pyrochlore with multi-elements at a site

In this work, the irradiation response of A2Ti2O7 (A represents rare earth elements of Gd, Dy, Ho, Er, Yb and Nd) series ceramics were systematically studied under 3 MeV Au2+ ions. The structural changes pre- and post-irradiation were characterized using X-ray diffraction (XRD), grazing incidence X-ray diffraction (GIXRD) and Raman spectroscopy. After heavy ion irradiation, all the samples undergo structural transformations from ordered pyrochlore to disordered fluorite and then to amorphous phase. The sample surface became fully amorphous when exposed to the maximum irradiation dose. The 5RETO high-entropy pyrochlore exhibits the lowest rate of amorphization during the process of structural transformation. The cation radius ratio and mixed entropy are the primary factors influencing amorphization rate. The cation radius ratio shows a strong positive correlation with the amorphization rate, while the mixed entropy demonstrates a weak negative correlation with the amorphization rate. The cation radius ratio can thus serve as a reliable indicator for predicting the radiation resistance of high-entropy pyrochlore ceramics.

Transformation of refractory ceramic MgAl2O4 into blue light emitting nanomaterials by Sr2+/Cr3+ activation

The current research aims at manipulation of physical properties of spinel MgAl2O4 by substitution of Sr2+ cations at tetrahedral and Cr3+ at orthogonal-sites. Synthesized materials were studied by XRD, TGA, SEM, EDX and UV–visible, diffuse reflectance and photoluminescence spectroscopy. A series of Sr2+ and Cr3+ doped derivatives with the general formula Mg1-xSrxAl2-yCryO4 (where x, y = 0.2, 0.4, 0.6, 0.8 and 1.0) have been produced and investigated using the co precipitation technique. Although strain in the cubic crystal structure of magnesium aluminate spinel was seen upon doping due to Sr2+'s higher cationic radius, the structure remained reserved (spinel) for low dopant concentration (x, y = 0.2, 0.4, 0.6). The behavior of activator ions Cr3+ in these derivatives is supposed to be altered due to change in site occupancy. Due to presence of antisites defects activator ions; structural, optical, thermal, electrical properties of MgAl2O4 material were modified.