Cation Sites Research Articles

Influence of Mg doping on structure and optical properties of red-emitting phosphor Li2TiO3:Mn4+

Li2TiO3:Mn4+ has been previously identified as a potential candidate to replace commercial red-emitting Eu2+-activated phosphors. Its luminescent efficiency is limited by the presence of defects and the sensitivity of Mn4+ to redox processes. A series of co-doped Li2TiO3: x Mg2+, 0.01 Mn4+ samples were prepared to gain insight on the effect of electron doping on the structure and photoluminescent properties, through characterization by powder X-ray diffraction, elemental analysis, and optical spectroscopy. As Mg2+ substitutes for Li+, the ordered arrangement of cations within the honeycomb layers in the parent structure (Li2SnO3-type, an ordered derivative of rocksalt) gradually transforms to a more disordered arrangement. The increased cation site disorder leads to less intense and broader emission peaks as well as lower quantum yields.

Enhanced thermoelectric performance of n-type Mg3.2Sb1.5Bi0.5 by rare-earth elements (Er, Tb, Tm) doping into Mg site

The n-type Mg3.2Sb1.5Bi0.5 has emerged as a promising candidate for thermoelectric materials and has attracted significant research interest. However, effective n-type dopants have been predominantly limited to chalcogens. In our work, we found that rare-earth elements (Er, Tb, Tm) are highly effective dopants for n-type Mg3.2Sb1.5Bi0.5. Through a combination of theoretical predictions and experimental validations, we demonstrate that these dopants significantly enhance the carrier concentration, leading to improved thermoelectric performance. Specifically, we employed direct ball milling and spark plasma sintering to introduce rare-earth elements at the Mg sites. Experimental results show that doping rare-earth elements in n-type Mg3.2Sb1.5Bi0.5 has a higher carrier concentration ( ≈ 8.4 × 1019 cm−3), which is higher than that of chalcogen-doped samples ( ≈ 2 × 1019 cm−3). High power factor (S2σ) ≈ 16 μW cm−1K−2 was obtained in rare-earth elements (Er, Tb, Tm) doped samples. Combined with the lowered lattice thermal conductivity due to the introduction of effective phonon scattering centers in Mg3.2−xAxSb1.5Bi0.5 (A= Er, Tb, Tm) sample. Finally, the ZT values of all doped samples reached ≈ 1.44 at 750 K. The highest peak ZT is ≈ 1.65 at 750 K for Mg3.195Er0.005Sb1.5Bi0.5. The rare-earth elements (Er, Tb, Tm) doped n-type Mg3Sb1.5Bi0.5 has comparable thermoelectric performance with the chalcogen-doped n-type Mg3Sb1.5Bi0.5, exhibiting promising potential for practical applications. This present work offers a comprehensive understanding of the effect of cation site doping improves the thermoelectric properties of n-type Mg3Sb2.

Enhancing Electrochemical Sensor Performance: Studies of Electrodes Tailored with ZnO/ZnFe2O4 Nanoparticles

Spinel metal oxides possess excellent magnetic, electrical, and optical properties. They take AB2O4 (face centered cubic) form with oxygen anions providing tetrahedral (Td) and octahedral (Oh) sites for A+2 and B+3 cations. Spinel can have a normal, inverse, or mixed form based on the occupancy of different cations in Td and Oh sites. The peculiarity of the spinel crystal structure is that its composition can be easily modified without affecting the crystal structure based on the type of cation. The type of cation in the composition defines if the spinel has a normal or inverse form [1]. Based on these premises, we have already synthesized ZnxNi1-xFe2O4 (x =0, 0.2, 0.4, 0.6, 0.8, 1) nanomaterials achieving a clear gradual transition from inverse (x=0) to normal (x=1) spinel. Synthesized nanomaterials were employed as mediators in electron transfer between the screen-printed carbon working electrode and paracetamol to understand the effect of chemical composition and crystal structure on the electron transfer at the electrochemical interface [1]. Normal spinel ZnFe2O4 was found to be the best nanomaterial in terms of sensitivity and kinetic rate constant. In further works, with the aim to understand the effect of ionic radii on sensitivity and electron transfer rate constant in electrochemical sensing of paracetamol, we have focused on the normal spinel structure and modified the composition by varying the concentration of Fe3+ with Cr3+ and Bi3+ [2,3]. This study also proved that the normal spinel ZnFe2O4 has the highest sensitivity and electron transfer rate constant towards paracetamol sensing.In this work, we will present the synergic effect that can be obtained by interfacing ZnFe2O4 with ZnO nanomaterials by tuning the band gap of the heterogeneous structure. The aim is to understand the effect of band gap on sensitivity and electron transfer rate constant in electrochemical sensing. ZnFe2O4, ZnO, and ZnO/ZnFe2O4 nanomaterials are synthesized by a simple, single step auto combustion technique using the respective metal nitrates as precursors. Nanomaterial morphology and particles size are investigated by scanning electron microscopy. X-ray diffraction technique is employed to analyze the crystal structure and identify different phases in the newly synthesized materials. Then, commercially available screen-printed carbon electrodes with carbon working electrode and carbon counter electrodes are used for the electrochemical measurements in combination with an external double junction Ag/AgCl as a reference electrode. The synthesized nanomaterials are mixed with 1-butanol and a 5 μL solution is used to modify the surface of the carbon working electrode to mediate the redox reactions between the carbon surface and the molecule of interest. Primarily the sensors are characterized using cyclic voltammetry with ferri/ferrocyanide redox couple as a probe molecule. Improvement in sensitivity is observed for ZnFe2O4 (8.85 ± 0.50 μA/mM), ZnO (8.50 ± 0.30 μA/mM), and ZnO/ZnFe2O4 (8.22 ± 0.16 μA/mM) sensors compared to the bare carbon one (6.30 ± 0.40 μA/mM). By performing cyclic voltammetry at different scan rates (ν) from 25 to 125 mV/s, a good linearity of redox currents with respect to v0.5 is observed and redox peak positions are varying linearly with ln(ν). Peak-to-peak separation (ΔEp) is reduced for ZnO/ZnFe2O4 sensors compared to the carbon one. All these results suggest a faster electron transfer at the interface when the modified electrodes are used. Laviron model is employed to calculate the electron transfer rate coefficient and constant. The rate constant for ZnFe2O4 (41.8 ± 2.6 ms-1), ZnO (46.0 ± 4.0 ms-1), and ZnO/ZnFe2O4 (33.1 ± 4.5 ms-1) sensors is 3 to 5 times higher as compared to the bare carbon one (9.97 ± 0.78 ms-1). We are currently studying the potential application of ZnO/ZnFe2O4 nanomaterials in electrochemical sensing of small molecules relevant in biomedical field (dissolved oxygen, pH) and pharmaceutical drugs (paracetamol) to assess the potential for their use in different clinical settings.

Improving thermodynamic stability of double perovskites with machine learning: The role of cation composition

Perovskite materials have exhibited promising potential in various fields, including solar cells, photodetectors, and light-emitting devices, owing to their exceptional optoelectronic properties and low-cost synthesis methods. In this work, the quest for thermodynamic stability in perovskite materials for optoelectronic applications is addressed through a machine learning (ML) approach. We also analyzed the importance of cations in the stability of double perovskites. It was found that the AUC (area under the curve) and accuracy of the LightGBM model in classification are 0.918 and 0.92, respectively, and the RMSE (root mean square error) and R2-score in regression are 0.119 and 0.872, respectively. Subsequently, the model was used to predict the properties of 10 new perovskites with high accuracy. Finally, the analysis of cationic sites revealed that the stability of the double perovskite is significantly affected by the elements occupying the A, B, and B’ sites. Our results provide an optimal machine learning approach for discerning the thermodynamic stability of double perovskites, which can be a useful guide for tuning the properties of perovskite materials.

Suppressing the phase separation in FAMA mixed perovskite solar cells via the preloading of A site cations within the lattice

The incorporation of MA as a dopant is highly advantageous for stabilizing the lattice structure of α-phase FAPbI3. However, achieving a homogeneous phase mixing is only feasible at elevated MA doping levels, which significantly compromises both the efficiency and stability of FA-dominated perovskite solar cells (PSCs). In this study, it is found that in the nucleation stage of FAMA mixed perovskite, MA+ exhibit a significant kinetic advantage over FA+ in their reaction with PbI3−. The rapid crystallization of MAPbI3 not only induces FA-MA separation but also hinders the crystallization of perovskite due to strains induced by the bulky FA+ cations. To address this issue, we introduced FA0.8MA0.2PbI3 single crystals as the material source to prepare the precursor solutions, which achieved a delicate balance between lattice stability and bandgap (Eg = 1.54 eV). The preloaded A-site cations within the PbI3− cages make the bare FA-dominated perovskite films by blade coating maintain the phase stability in wild ambient for over one year. The final PSCs (0.09 cm2) achieved a highest power conversion efficiency (PCE) of 23.66 %, among the highest efficiency records for blade coated PSCs. The unpackaged PSCs show efficiency loss of < 10 % as being aged in air with a relative humidity of 10 % for over 1000 h.

Highly ordered Periodic Mesoporous Organosilica material containing the ionic 4,4-bipyridinium group and decorated with palladium nanoparticles: A proposal for nanoreactor

A Periodic Mesoporous Organosilica (PMO) containing the cationic 4,4-bipyridinium group, presenting 0.25 mmol g−1 that corresponds to 11.5 w/w%, was successfully prepared. This material was designed to have the ionic group acting as anchoring agent of PdCl42- anion complex, in a much lower amount than the available cationic sites (3 and 15 molar%). Subsequently, the palladium complex was in situ reduced to obtain stabilized palladium nanoparticles (PdNP). The ensemble of characterization results showed that the PMO material walls have a cylindrical morphology with hexagonal packing, generating well-ordered pores with a narrow size distribution and high surface area, even after being decorated with PdNP. This material is a candidate to be an efficient nanoreactor considering that it contains spatial uniformity in its chemical sites and confined environment. Aiming to evaluate the availability of palladium sites, the material was used as a catalyst in the reduction of p-nitrophenol model reaction. Although the catalyst of the present study has a comparable activity with other already reported systems, it presents the impressive lowest molar palladium/p-nitrophenol ratio found in literature.

Is the Presence of Sn2+ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Comprehending the relationship between crystal structures and transport properties is crucial to develop materials with improved electrical and thermal properties for thermoelectric applications. In this article, we report on the complex crystal structure and physical properties of Cr2Sn3S7, a n-type magnetic semiconductor with a low energy band gap and low thermal conductivity. Importantly, we demonstrate that the high level of structural complexity is related to the coexistence of two sublattices: a host lattice, [Cr4Sn2S11]2-, characterized by a mixed Sn4+/Cr3+ occupancy of its cationic sites, and a guest lattice characterized by [Sn4S3]2+ chains, containing Sn2+ cations only, closely related to the ones encountered in the orthorhombic SnS compound. By combining experiments including X-ray diffraction with ab initio calculations of electrons and phonons, we succeeded to elucidate the origin of the low thermal conductivity in Cr2Sn3S7. We demonstrate that the low dimensionality of the [Sn4S3]2+ chains, which generates weak Sn···S interactions with the 3D host lattice, is induced by the lone pair stereochemical activity of Sn2+. This lattice softening favors strong anisotropic vibrations at low frequencies, highlighting the primordial role played by Sn2+ cations in both crystal structure dimensionality and low thermal conductivity in tin-based sulfides.

High-resolution yeast actin structures indicate the molecular mechanism of actin filament stiffening by cations

Actin filament assembly and the regulation of its mechanical properties are fundamental processes essential for eukaryotic cell function. Residue E167 in vertebrate actins forms an inter-subunit salt bridge with residue K61 of the adjacent subunit. Saccharomyces cerevisiae actin filaments are more flexible than vertebrate filaments and have an alanine at this position (A167). Substitution of this alanine for a glutamic acid (A167E) confers Saccharomyces cerevisiae actin filaments with salt-dependent stiffness similar to vertebrate actins. We developed an optimized cryogenic electron microscopy workflow refining sample preparation and vitrification to obtain near-atomic resolution structures of wild-type and A167E mutant Saccharomyces cerevisiae actin filaments. The difference between these structures allowed us to pinpoint the potential binding site of a filament-associated cation that controls the stiffness of the filaments in vertebrate and A167E Saccharomyces cerevisiae actins. Through an analysis of previously published high-resolution reconstructions of vertebrate actin filaments, along with a newly determined high-resolution vertebrate actin structure in the absence of potassium, we identified a unique peak near residue 167 consistent with the binding of a magnesium ion. Our findings show how magnesium can contribute to filament stiffening by directly bridging actin subunits and allosterically affecting the orientation of the DNase-I binding loop of actin, which plays a regulatory role in modulating actin filament stiffness and interactions with regulatory proteins.

Beyond Cation Disorder: Site Symmetry‐Tuned Optoelectronic Properties of the Ternary Nitride Photoabsorber ZrTaN3

AbstractTernary nitrides are rapidly emerging as promising compounds for optoelectronic and energy conversion applications, yet comparatively little of this vast composition space has been explored. Furthermore, the crystal structures of these compounds can exhibit a significant amount of disorder, the consequences of which are not yet well understood. Here, the deposition of bixbyite‐type ZrTaN3 thin films is demonstrated by reactive magnetron co‐sputtering and observed semiconducting character, with a strong optical absorption onset at 1.8 eV and significant photoactivity, with prospective application as functional photoanodes. It is found that Wyckoff‐site occupancy of cations is a critical factor in determining these beneficial optoelectronic properties. First‐principles calculations show that cation disorder leads to minor deviations in the total energy but modulates the bandgap by 0.5 eV, changing orbital hybridization of valence and conduction band states. In addition to demonstrating that ZrTaN3 is a promising visible light‐absorbing semiconductor and active photoanode material, the findings provide important insights regarding the role of cation ordering on the electronic structure of ternary semiconductors. In particular, it is shown that not only cation order, but also the cationic Wyckoff site occupancy has a substantial impact on key optoelectronic properties, which can guide future design and synthesis of advanced semiconductors.

Synthesis of Zintl Phase Metal Silicide Thermoelectric Materials in Magnesium/Zinc Flux.

Zintl phases have potential applications as thermoelectric materials for power generation and cooling owing to their complex crystal structures and unique electronic properties. We carried out reactions of silicon with barium and strontium in excess Mg/Zn flux to synthesize (Ba/Sr)5+xMg19-xSi12 Zintl phases, investigating the effect of varying Ba/Sr ratio on site mixing and thermoelectric properties. (Ba/Sr)5+xMg19-xSi12 compounds with 0 < x < 3 are charge-balanced Zintl phases which adopt the hexagonal Ho5Ni19P12 structure type (space group P6̅2m). Density of states calculations indicate that these materials are semimetals. Single-crystal X-ray diffraction data and elemental analysis for Ba5Mg19Si12, Ba4.86Sr2.94Mg16.20Si12, Ba3.63Sr4.20Mg16.17Si12, Ba1.93Sr5.99Mg16.08Si12, and Sr7.82Mg16.18Si12 show occupation of barium and strontium cations in Ho sites, while strontium mixes with magnesium on a specific Ni site. Powder XRD data of products show that they are single phase throughout the sample. Thermoelectric measurements indicate that increasing strontium content and mixing on three cation sites decreases thermal conductivity; it is hypothesized that improved overall thermoelectric behavior is likely due to the rattling of the Sr cations in their positions.

Compact Polyelectrolyte Complexes of Poly(l-Lysine) and Anionic Polysaccharides.

Compact polyelectrolyte complexes (CoPECs) can exhibit mechanical properties similar to those of biological tissues and other interesting properties, such as self-healing. To date, a variety of CoPECs prepared from synthetic polyelectrolytes have been investigated, but there are very few examples based entirely on biopolymers. We describe here an investigation of CoPECs based on poly(l-lysine) (PLL) with sodium hyaluronate (HA) and alginate (Alg). A 2:1 ratio of cation:anion and 0.25 M NaBr was beneficial for the formation of viscoelastic PLL-HA CoPECs, with the favorable ratio attributed to the spacing of carboxylates on HA being one every two saccharide units. In contrast, 1.0 M NaBr and a 1:1 ratio were better for PLL-Alg CoPECs. Both CoPECs swelled or retained a constant volume when immersed in hypertonic media, but contracted in hypotonic media. The loading of molecules into the PLL-HA (2:1) CoPECs was investigated. Higher loadings were achieved for anionic molecules compared to cations, presumably due to the excess cationic binding sites on the networks. The times required for full release of the molecules ranged from less than 2 h for neutral paracetamol to about 48 h for crystal violet and diclofenac.

Structure of ZnxFe3−xO4 nanoparticles studied by neutron diffraction and its relation with their response in magnetic hyperthermia experiments

The mixed zinc-ferrite spinel magnetic nanoparticles (MNPs) with the general formula ZnxFe3−xO4 are among the most extensively studied families of Fe oxides due to their interesting and diverse chemical, electronic, and magnetic properties. These systems offer the possibility of surface functionalization and possess high biocompatibility, making them highly attractive for applications in biomedicine, such as magnetic fluid hyperthermia (MFH). The efficiency of the MFH process relies on the magnetic, structural and morphological properties of the MNPs. The substitution with the Zn ion and the cationic distribution, as well as the synthesis process employed, have a direct impact on the final properties of these oxides. Therefore, it is essential to have tools that enable a comprehensive characterization of the system to assess its performance in MFH. In this study, we have synthesized four ZnxFe3−xO4 MNP systems using three different methods: two by thermal decomposition at high temperatures, one by co-precipitation, and another by co-precipitation followed by ball milling. We analyze the effect of these various synthesis processes on the magnetic and crystallographic properties, aiming to correlate them with the response of each system in MFH. Neutron diffraction data are employed to determine the cation site occupation and to investigate the correlation with the synthesis method. MFH measurements were conducted in media of diverse viscosities, revealing different values of specific loss power, thus demonstrating a clear dependence on the synthesis process and Zn content.

Synergistic Crystallization Modulation and Defects Passivation in Kesterite via Anion-Coordinate Precursor Engineering for Efficient Solar Cells.

It has been validated that enhancing crystallinity and passivating the deep-level defect are critical for improving the device performance of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. Coordination chemistry interactions within the Cu-Zn-Sn-S precursor solution play a crucial role in the management of structural defects and the crystallization kinetics of CZTSSe thin films. Therefore, regulating the coordination environment of anion and cation in the precursor solution to control the formation process of precursor films is a major challenge at present. Herein, a synergetic crystallization modulation and defect passivation method is developed using P2S5 as an additive in the CZTS precursor solution to optimize the coordination structure and improve the crystallization process. The alignment of theoretical assessments with experimental observations confirms the ability of the P2S5 molecule to coordinate with the metal cation sites of CZTS precursor films, especially more liable to the Zn2+, effectively passivating the Zn-related defects, thereby significantly reducing the defect density in CZTSSe absorbers. As a result, the device with a power conversion efficiency of 14.36% has been achieved. This work provides an unprecedented strategy for fabricating high-quality thin films by anion-coordinate regulation and a novel route for realizing efficient CZTSSe solar cells.

Influences of the spacing between nitrogen atoms on tribological performance of dual active site phosphorus-nitrogen (P-N) ionic liquid

Four dual active site ionic liquids (ILs): N2NP0, N4NP0, N6NP0, N10NP0 and three single active site ILs: N2P0, N3P0, N8P0 were synthesized successfully, furthermore, anti-wear and extreme pressure properties of the additives were tested with 0.5 wt% concentration in PAO10 base oil. The results showed that N6NP0 with carbon chain length of six between the nitrogen atoms exhibits the best tribological performance (The wear scar diameter is 0.39 mm, the values of PB (the last non-seizure loads) and PD (weld points) were 135 Kgf and 200 Kgf, respectively), which is mainly attributed to the formed thicker tribo-film (thickness of 50–60 nm) on the friction surface. Through analyzing the tribological morphology, chemical composition and tribo-film microstructure of wear scars surface by SEM-EDS, 3D profile, AFM, XPS and FIB-TEM, the lubrication mechanism of ILs was revealed. Furthermore, density functional theory (DFT) calculations confirmed that the tribological performance of dual active site ionic liquid additives depend strongly on their molecular configuration. It was found that rational adjustment of the length of the ILs cationic active site linkage group results in a reduction of the steric hindrance of the entire molecule. This study will help to guide the design of ILs with good tribological performance and low phosphorus content.

Compositional-Dependent Structural Parameters and Energetics of Hibonite: Quantum-Chemical Investigation.

One of the first minerals to condense from the early solar nebula was hibonite (CaAl12O19), demonstrating a hexagonal crystal structure. There are five unique aluminum cation sites (M1-M5) in hibonite. Although hibonite contains aluminum, it can also have 3d transitional metals that substitute at aluminum cation sites, such as titanium, and other metals such as magnesium. Titanium can occur in multiple oxidation states, linking to redox conditions. A single substitution occurs when a single aluminum atom is replaced by a single titanium atom, causing the Ti to take on a 3+ oxidation state. On the other hand, Ti achieves an oxidation state of 4+ during a double substitution when a pair of aluminum atoms is replaced by a titanium and a magnesium atom. A density functional theory-based calculation is used to explore the relationship between the number of substitutions and the lattice parameters of the hibonite crystal. The calculated results reveal that the lengths of both unit cells (a and c) increase with an increasing number of single or double substitutions. The rate of increment per substitution depends on the cation sites, M1-M5, and substitution types. Along with the expansion of the unit cell of the hibonite due to the substitution, the substituted unit cell gains energy (and in turn stability) compared to the substituted unit cell without expansion, dependent on the lattice site and substitutions.

Synthesis, crystal and electronic structures of two novel tunnel bismuth oxychlorides Bi18O22Cl8.5(BO3)0.5 and Bi18O22Cl8Se

Single crystals of two new quaternary bismuth oxychlorides, Bi18O22Cl8.5(BO3)0.5(1) and Bi18O22Cl8Se (2), have been serendipitously produced in syntheses starting from bismuth borate or oxyselenide and oxychloride. The crystal structure of 1 represents a high symmetry analog of the PbBi17O22Cl9 type structure, formed by double aliovalent (Pb2+ → Bi3+, 0.5Cl– → 0.5BO33−) substitution at the two respective cationic and anionic sites, while 2 is a full structural analog of PbBi17O22Cl9. Overall, their structures can be described as sequences of thick (16 Å) slabs (2D “host” structure) comprised of litharge–like layers and ribbons formed by edge-sharing oxocentered OBin, polyhedra (n = 4 and 5). The chloride anions fill the 7.6 Å channels with the triangular cross-section inside the slabs as well as the interlayer space wherein they are partially substituted by disordered BO33− groups or Se2− anions. Compound 1 is just the second example of a mixed halide–borate occupancy among bismuth compounds while 2 illustrates much broader perspectives of mixed oxyhalide–oxychalcogenide approach to construction of novel complex bismuth compounds. Both compounds make new contributions to the family of tunnel structures of anion-centered tetrahedra featuring wide trigonal channels filled by halide anions or more complex metal–halide “salt inclusions”.

Zhengminghuaite, Cu6Fe3As4S12, a new sulfosalt mineral from the Zimudang Carlin-type gold deposit in southwestern Guizhou, China

Abstract Zhengminghuaite, ideally Cu6Fe3As4S12, is a new Cu-Fe arsenosulfosalt found in the Zimudang Carlin-type gold deposit in southwestern Guizhou, China. It occurs as irregular, commonly fractured grains of several to a few tens of micrometers in the brecciated gold ores and is paragenetically associated with the late ore-stage mineral assemblage, including realgar, orpiment, pyrite, chalcopyrite, arsenopyrite, aktashite, christite, quartz, and calcite. Zhengminghuaite is opaque with a metallic luster and a conchoidal or uneven fracture. The Vickers microhardness (VHN10) is 219 kg/mm2 (range 192–247 kg/mm2), and the calculated density is 4.77(5) g/cm3. In reflected light, zhengminghuaite is whitish gray with weak bireflectance (whitish gray to pinkish tinted gray), very weak anisotropy, and no internal reflection. Electron microprobe analyses give the empirical formula (Cu5.92Hg0.08)Σ6.00 (Fe1.59Hg1.07Zn0.37)Σ3.03(As3.94Sb0.02)Σ3.96S11.93 on the basis of total cations = 13, with the simplified formula Cu6(Fe,Hg,Zn)3(As,Sb)4S12. Zhengminghuaite is trigonal, with space group R3. Unit-cell parameters determined from the single-crystal X-ray diffraction data are as follows: a = 13.5373(17) Å, c = 9.2354(13) Å, and V = 1465.7(4) Å3 (Z = 3). The eight strongest lines in the X-ray diffraction pattern are [d (Å) (I, %) (hkl)]: 3.0785 (67) (003), 3.0670 (100) (131), 2.6586 (89) (132), 1.8825 (97) (134), 1.8773 (82) (520), 1.6060 (89) (135), 1.6028 (81) (523), and 1.6012 (83) (261). The crystal structure of zhengminghuaite belongs to the nowackiite group and can be described as formed by (0001) layers composed of corner-sharing FeS4 and CuS4 tetrahedra that delimit two triangular cavities. Zhengminghuaite is the Fe-dominant analog at the divalent cations site of nowackiite (Cu6Zn3As4S12) and aktashite (Cu6Hg3As4S12). Paragenetic relationships indicate that zhengminghuaite and associated Hg- and Tlsulfosalts precipitated in response to the increase in sulfidation state and decrease in temperature of the late-ore stage hydrothermal fluid.

Discerning the role of a site cation in ACoO3 perovskites for boosting Co3+/Co2+ redox cycle for pollutant degradation: DFT calculation, mechanism and toxicity evolution

The degradation of persistent and refractory pollutants, particularly plastic and resins manufacturing wastewater, poses a significant challenge due to their high toxicity and high concentrations. This study developed a novel hybrid ACoO3 (A = La, Ce, Sr)/PMS perovskite system for the treatment of multicomponent (MCs; ACN, ACM and ACY) from synthetic resin manufacturing wastewater. Synthesized perovskites were characterized by various techniques i.e., BET, XRD, FESEM with EDAX, FTIR, TEM, XPS, EIS, and Tafel analysis. Perovskite LaCoO3 exhibited the highest degradation of MCs i.e., ACN (98.7%), ACM (86.3%), and ACY (56.4%), with consumption of PMS (95.2%) under the optimal operating conditions (LaCoO3 dose 0.8 g/L, PMS dose 2 g/L, pH 7.2 and reaction temperature 55 °C). The quantitative contribution (%) of reactive oxygen species (ROS) reveals that SO4•− are the dominating radical species, which contribute to ACN (58.3% for SO4•− radicals) and ACM degradation (46.4% for SO4•− radicals). The tafel plots and EIS spectra demonstrated that perovskites LaCoO3 have better charge transfer rates and more reactive sites that are favorable for PMS activation. Further, four major degradation pathways were proposed based on Fukui index calculations, as well as GC-MS characterization of intermediate byproducts. Based on a stability and reusability study, it was concluded that LaCoO3 perovskites are highly stable, and minimal cobalt leaching occurs (0.96 mg/L) after four cycles. The eco-toxicity assessment performed using QSAR model indicated that the byproducts of the LaCoO3/PMS system are non-toxic nature to common organism (i.e., fish, daphnids and green algae). In addition, the cost of the hybrid LaCoO3/PMS system in a single cycle was estimated to be $34.79 per cubic meter of resin wastewater.

Effect of cation site occupancy on the structure and magnetic properties of SrCoxTixFe12–2xO19 thin films

Multiferroic materials have potential applications in multifunctional electronic devices, and M-type hexaferrite with conical spin order is a promising candidate. In this paper, a series of SrCoxTixFe12–2xO19 thin films were prepared by a sol-gel method, and x-dependent structure, cation site occupancy and magnetic properties were investigated to explore the origin of conical spin order in M-type hexaferrite. It was found that the introduction of Co2+ and Ti4+ ions decreases the uniaxial magnetocrystalline anisotropy and breaks the threefold symmetry of the lattice, inducing a conical magnetic structure. Moreover, the appearance temperature of the conical spin order (Tcone) increases first and then decreases with the increase of x, and the largest Tcone of about 324 K is obtained in SrCo1.8Ti1.8Fe8.4O19 thin film. The evolution of magnetization is closely related to the site occupancy of Co2+ and Ti4+ ions, and the net effective substitution ratio of spin-down Fe3+ is positive correlation to the Tcone of SrCoxTixFe12–2xO19 and thus considered to be responsible for the introduction of conical spin order. The results reveal the correlation between the structure, magnetic properties and cation site occupancy, pointing out an effective method to induce conical spin order in M-type hexaferrites.

Bi3+-activated Na3Ca2TaO6: A novel narrow-band blue-emitting phosphor towards backlight display applications

Developing efficient and stable narrow-band blue phosphors has always been crucial for advancing LED backlighting technology. In this study, a host of Na3Ca2TaO6 with a strong rigid structure and high cationic site symmetry was selected, while Bi3+ was utilized as the activator. A novel narrow-band blue-emitting phosphor Na3Ca2TaO6:Bi3+ was obtained through high temperature solid phase sintering. The excitation peak of Na3Ca2TaO6:0.005Bi3+ is at 370 nm, which can effectively match the near-ultraviolet chip. Under near-ultraviolet light excitation, the Na3Ca2TaO6:0.005Bi3+ sample exhibits narrow-band blue emission, characterized by a dominant peak at 421 nm and a full width at half maximum of 47 nm. Additionally, Na3Ca2TaO6:Bi3+ demonstrates the color purity of 93.7 %, a quantum efficiency of 56.3 % and thermal stability of 80 %@150 °C. Based on crystal structure data, spectral data, and empirical formulas, it can be inferred that Bi3+ occupies the Na2 and Ca site and forms two luminous centers in Na3Ca2TaO6. When Na3Ca2TaO6:Bi3+ is utilized as the blue light component in WLED devices packaging, an impressive NTSC color gamut of 89.4 % can be achieved. The present study is anticipated to serve as a valuable point of reference for the future advancement of phosphors specifically tailored for backlight display applications.