Ion Substitution Research Articles

Effects of Ag ion substitution in zeolite and use of citric acid on the efficacy of antimicrobial properties of EVA‐PE composite films

Effects of <scp>Ag</scp> ion substitution in zeolite and use of citric acid on the efficacy of antimicrobial properties of <scp>EVA</scp>‐<scp>PE</scp> composite films

Net-shaping (Y,NSG)BCO composite superconductor into cylindrical geometry with enhanced flux pinning up to 9 T at 77 K

Abstract Fabrication of a (Y,RE)BCO superconducting compact simultaneous with improved properties is demonstrated using gelcasting of slurries into rapid prototyped precision moulds. The infiltration Growth (IG) process with NdBCO film seed was used to obtain a textured 45 mm long hollow superconducting (Y,RE)BCO cylinder, as a prototype. This involves design of a (Y,RE)2BaCuO5 preform referred to as (Y,RE)-211, into which liquid phase is infiltrated; this reacts with the preform and forms (Y,RE)Ba2Cu3O7-x. The end product aimed at is a composite of YBa2Cu3O7-x (YBCO) with 20 wt% of mixed rare earth (Nd,Sm,Gd)BCO and 0.5 wt% of WO3 nanoparticles, which are intended to cause notable enhancement in flux pinning and critical current density (J c). Uniform distribution of micron-sized (Y/RE)-211 and WO3 nanoparticles in the matrix was enabled by sol-casting process. Magnetic shielding is demonstrated at low dc fields (41 gauss). J c is found to remain nearly constant with field (B) at each temperature (T) up to 50 K, where J c reaches about 4 kA cm−2 at 8.5 T. At 77 K, J c of ∼ 4 kA cm−2 at zero field and ∼ 0.4 kA cm−2 at 8.5 T is observed. The flux pinning force density (F p) increased with the applied field, reaching a maximum at a field (B p) of 7 T to 8 T for all temperatures from 10 K to 77 K. Temperature-independent B p confirms that flux pinning is caused by structural defects that induce fluctuations in the Ginzberg-Landau parameter (k). Substitution of RE ions randomly at the Y-site in YBCO unit cells can locally create compositional fluctuations that lead to stress fields and a dense network of stacking faults and assist pinning of flux. Analysis of F p (B) by scaling laws does confirm δk pinning to be the dominant mechanism. A second peak observed in F p(B) curves at low fields, below 3 T, is attributed to additional pinning from WO3 nanoparticles and is field-dependent. Significance of the present process stems from the fact that it enables uniform distribution of second phase additions to be realized in the end product, for improved performance and it allows design and creation of components of composite ceramic superconductor in any complex shape, required for a chosen application.

Donnan Dialysis-based Approach for Reclamation of Waste Acid with a Low Concentration

This study provides a proof-of-concept investigation into the direct utilization of low-concentration recovered acid as a proton source for the efficient recovery of organic acids via Donnan dialysis, a scenario of particular significance in industrial parks. A primary objective is to examine the implications of waste acid concentration on the coupling process. To evaluate the technological feasibility, process simulations are performed utilizing a mathematical model grounded in the Nernst-Planck equation and associated equilibrium relationships. Furthermore, a variety of experimental conditions, encompassing different types of organic acids and varying concentrations of waste acid, are explored to analyze the ion substitution behaviors involved. The findings from both simulations and experiments indicate that weaker organic acids demonstrate superior performance, particularly regarding recovery rates and process efficiency. Additionally, it is revealed that merely increasing the concentration of the draw solution does not constitute an effective approach for improving the DD-based organic acid recovery process, thereby suggesting the potential for the direct application of low-concentration recovered acid. Given its significant advantages, the proposed DD-based coupling technology shows considerable promise for future applications.

Elastic and magnetic characteristics of nano-spinel ferrite Co0.5 MgxCu0.5−xFe2O4

Wet-chemical co-precipitation was used to create Co0.5MgxCu0.5−xFe2O4 nano-ferrites (x = 0.0, 0.2, 0.3, and 0.4). XRD, FT-IR, HRTEM, and EDX analyses were used to confirm each sample’s single-phase spinel cubic crystal structure. The crystallite size was calculated from the XRD data and determined to be between (11.1570 and 16.1457 nm), with a lattice constant between (8.359 to 8.387Å). The two absorption bands found in the FTIR data were utilized to show metal cation and oxygen bond stretching at tetrahedral and octahedral positions, as well as to calculate the elastic moduli. The elemental composition and structural behavior of every sample were examined using FE-SEM and EDS. The magnetic parameters were also estimated based on the VSM data, the contribution of magnetic anisotropy (K), and the magnetic interaction by Neel’s and Y-K-type magnetism modify as the Mg2+ ion substitution increases, thus we must consider how this variation in cation distribution affects all of these factors. As per the ferromagnet theory, ions originating from the magnetic tetrahedral A and octahedral B sites engage in super-exchange interactions with one another. Anti-ferromagnetic alignment occurs as a result (MB-MA). Magnetization occurs as a result.

Structural and magnetic studies of Cobalt-Substituted copper ferrites for efficient photocatalytic dye degradation

In this work, cobalt-substituted copper ferrites with the composition CoxCu1-xFe2O4 (0.0 ≤ x ≤ 1.0) were synthesized using the sol–gel autocombustion method with citric acid as fuel. The influence of cobalt ion substitution (Co2+) on the structural, magnetic, optical, and photocatalytic properties was systematically studied. A range of characterization techniques, including X-ray diffraction (XRD), infrared spectroscopy (FTIR), scanning electron microscopy (SEM), UV–visible spectroscopy, and vibrating sample magnetometry (VSM), were used to analyze the properties of the synthesized materials.XRD analysis revealed that the crystallite sizes of the samples ranged between 20–25 nm, with interplanar distances, bond lengths between cations, and crystallite size varying according to the degree of cobalt substitution. The formation of the spinel structure and the successful incorporation of cobalt ions into the lattice were confirmed by FTIR spectroscopy. Magnetic measurements showed that increasing the cobalt content enhanced the saturation magnetization while also influencing the Curie temperature and coercivity.The photocatalytic efficiency of the CoxCu1-xFe2O4 samples was evaluated for the degradation of Methylene Blue, Congo Red, and Malachite Green dyes under visible light irradiation. The photocatalytic degradation rates were strongly influenced by the copper-to-cobalt ion ratio, with cobalt-rich compositions demonstrating superior activity. The best photocatalytic performance was observed for intermediate cobalt concentrations (x = 0.4 and x = 0.6), where particle size and dielectric constant behavior led to efficient electron-hole separation and improved degradation rates. Methylene Blue decomposition was significantly enhanced in an alkaline medium (pH10) due to better adsorption and charge interaction between the dye and the photocatalyst surface. Fitting the experimental data to the Langmuir-Hinshelwood and Weibull models further highlighted the increased degradation rates with increasing pH and cobalt content, supporting the conclusion that cobalt-substituted copper ferrites are highly effective photocatalysts.

Electro-activated peroxymonosulfate based on hollow cubic skeleton nanoflower cathode catalyst MoSe2/cubic nanocage (CNC) for enhanced degradation of norfloxacin: Performance, mechanism, degradation pathways and toxicity

Recently, antibiotic wastewater pollution has become increasingly serious. In this study, a novel hollow cubic framework self-supported nanoflower-like cathode catalyst (MoSe2/CNC) based on Co Fe prussian blue analogues (CoFePBA)-derived cubic nanocage (CNC) loaded with MoSe2 was successfully prepared and utilized in an electro-activated peroxymonosulfate (PMS) system for norfloxacin (NOR) degradation. Benefit from the combined structures of MoSe2, MoC, and Co/FeNC, the electrocatalytic activity and specific surface area were greatly improved. The effects of catalyst dosage and ratio, current, PMS concentration, electrolyte type, pH, as well as initial concentration were comprehensively investigated. Under the optimal conditions, NOR and TOC removal reached 92.70% and 82.17%, respectively, which was superior to the previous studies. Additionally, ·O2− was proved to be the primary reactive species for NOR degradation.·Based on density functional theory (DFT) and intermediates analysis, NOR underwent substitution and ring-opening reactions in the piperazine ring, substitution of fluoride ions, and cleavage of the carboxyl group and tetrahydropyridine ring, ultimately converting into water, carbon dioxide, and inorganic ions. Moreover, toxicity assessment and seed germination experiments demonstrated that the toxicity of NOR and intermediates were strongly decreased by electro-activated PMS system based on MoSe2/CNC cathode. Overall, this study not only contributes to the evolution of efficient and sustainable wastewater purification technology, but also provides valuable insights into the degradation of antibiotic wastewater.

Ionic substitution through bredigite doping for microstructure and performance adjustment in DLP 3D-printed TPMS porous HA bone scaffolds

ABSTRACT Hydroxyapatite (HA) is widely used in bone scaffold development, but still faces problems of forming difficulty, slow degradation, and limited biological performance. In this study, triply periodic minimal surface (TPMS) porous HA scaffolds were prepared using desktop-level DLP and then doped with bredigite (BR) to enhance their performance through ion substitution to adjust microstructure. The DLP-prepared scaffolds displayed intricate curved surface porous structure, and their micro-porosity decreased while grain size increased with sintering holding time. During sintering, Mg2+ from BR substituted Ca2+ in HA, forming new secondary phases, which slightly decreased grain size while significantly increased micro-porosity. These factors slightly reduced mechanical properties while significantly enhanced degradation. The rapid release of inorganic active ions from BR and new phases enhanced the biomineralization and cell response. This study demonstrated the potential of using desktop-level DLP to construct complex porous ceramic scaffolds and using ion substitution to modulate their microstructure and performance.

A novel NASICON-typed Na3V1.96Cr0.03Mn0.01(PO4)2F3 cathode for high-performance Na-ion batteries

Na3V2(PO4)2F3 (NVPF) with a NASICON structure has attracted widespread attention as a cathode material for sodium-ion batteries due to its stable 3d open framework, high operating voltage, and high theoretical energy density. However, this material faces limitations in practical applications due to its inherently low intrinsic electronic conductivity and the high cost of vanadium. In this study, we substituted vanadium with low-cost elements and synthesized a series of NVPF cathode materials with varying levels of Cr/Mn doping using a simple sol-gel method. The optimal NVPF-Cr/Mn1 cathode exhibits discharge specific capacities of 119.7 mAh g−1 at 1C and 109.8 mAh g−1 at 10C. Additionally, the discharge specific capacity of NVPF-Cr/Mn1 is 106.9 mAh g−1, with a capacity retention rate of 80 % after 400 cycles. These performance improvements are attributed to the synergistic effect of co-doping with chromium (Cr) and manganese (Mn): they expand the channels for sodium ion transport within the lattice, reduce the material's impedance and polarization, enhance the kinetics of sodium ion diffusion reactions, effectively prevent lattice distortion, and significantly improve long-term cycling performance. By strategically designing NASICON-type cathodes and employing multi-metal ion substitutions to regulate composition, we not only enhance the battery's cycle life but also contribute to reducing the cost of electrode materials. This approach opens up new possibilities for practical applications in the field of energy storage.

Optimized electrostrain with minimal hysteresis at the MPB in BNT-based ceramics

Lead-free (Bi0.5Na0.5)TiO3 (BNT)-based ceramics play a vital role in transducers and sensors, owing to their pronounced electrostrain response under applied electric fields. This work presents a notable electrostrain response of 0.54 % with minimal electrostrain hysteresis (11 %) in the x = 0.30 composition near the morphotropic phase boundary (MPB) within (1–x)BNT-x(Ba0.15Sr0.55Ca0.3)TiO3 (x = 0.2–0.4, BNT-xBSCT) ceramics. By exploiting the variation in tolerance factor through titanate doping and localized disorder from A-site multiple ion substitution, we achieved enhanced electrostrain response via the evolution of nonergodic relaxor (NR) and ergodic relaxor (ER) phase boundaries. Notably, the x = 0.30 composition exhibits ultrahigh electrostrain (>0.5 %) with remarkable thermal stability above 70 °C. This stability arises from the combined effects of domain flipping in ER/NR mixed phases and reversible electric field-induced relaxor-to-ferroelectric phase transitions. These results hold significant potential for advancing electrostrain performance and thermal stability in lead-free BNT-based ceramics.

A Porphyrin-Based MOF Thin Film with Oriented Nanosheet Arrays for Optimizing a Nonlinear Optical Response.

Developing two-dimensional (2D) hybrid nanosheet arrays integrating inorganic and organic components is highly significant for third-order nonlinear optical (NLO) applications. Herein, an oriented 2D porphyrin-based MOF (ZnTPyP(Co)) thin film composed of vertically stacked ultrathin nanosheets was fabricated via the liquid-phase epitaxial (LPE) layer-by-layer (LBL) method. The prepared ZnTPyP(Co) thin film exhibits an outstanding third-order NLO response with a high third-order nonlinear susceptibility of ∼2.63 × 10-7 esu, which is ascribed to the hybrid nanosheet array structure. Additionally, experimental Z-scan measurement and theoretical calculations also demonstrate that the substitution of Co metal ions in the porphyrinic core can increase the level of delocalization of the porphyrinic group and contribute to the material's enhanced NLO properties. These findings not only provide new film candidates for NLO application but also highlight the potential of 2D MOF nanosheets in advanced optical devices.

Structural, Electronic, and Magnetic Properties of Gd-Substituted Bi2Fe4O9 Multiferroic: A Combined Experimental and DFT Approach

Abstract We present the structural, electronic, and magnetic properties of Gd3+ substituted Bi2Fe4O9 (BFO) via experimental analysis as well as density functional theory (DFT). Rietveld refined X-ray diffraction data shows phase purity of the samples having orthorhombic phase with space group: ‘Pbam’. Gd3+ ions substitution at Bi3+-site is confirmed by the shift in peaks ((002) and (220)) at higher 2θ angles as well as the reduction in lattice parameters. The PBE+U calculations predict a band gap of 1.76 eV (BFO) and 1.6 eV (Gd substituted BFO) which is in close agreement with the experimental values. This reduction in band gap due to Gd3+ substitution enhances conduction in substituted samples. The calculated density of states illustrates considerable hybridization between Fe-3d and O-2p states with substantial overlap among the Bi-6p and O-2p states. Incorporating Gd3+ ions further introduces additional exchange interactions between Gd-Fet and Gd-Feo, thus leading to enhanced magnetization as well as an increase in antiferromagnetic transition temperature (TN). This characteristic feature is supported by temperature-dependent magnetic susceptibility (χ) and dχ/dT plots. Hence, our experimental and theoretical findings suggest that BFO and its substituted samples are potential multiferroic materials for various device applications.

Effect of rare earth doping on structural, morphological, optical, and magnetic properties of the Y1-x(Gd, Dy)xBaCuFeO5 (x = 0.2, 0.4, 0.6, and 0.8) ceramics

The effect of the rare earth (RE) ion substitution on the structural, morphological, optical and magnetic properties of the Y1-xRExBaCuFeO5 (RE = Gd, Dy; x = 0.2, 0.4, 0.6, and 0.8) multiferroic compounds grown by the solid-state reaction is evaluated using X-ray diffraction (XRD), scanning electron microscopy (SEM), dispersive X-ray spectroscopy (EDX), reflectance spectroscopy techniques diffuse (UV–vis–NIR) and vibrating sample magnetometry (VSM). The results indicate that the RE substitution led to growth of single-phase materials, with a tetragonal structure and P4mm symmetry. The morphological analysis shows the formation of polycrystalline materials composed of grains of various shapes and sizes. Furthermore, the compositional analysis reveals that the materials do not present elements other than those used in the synthesis. The band gap (Eg) is tuned from 0.88 to 0.90 eV upon RE substitution. The magnetization curves obtained in the Zero-Field-Cooled/Field-Cooled (ZFC-FC) modes between 50 and 390 K, reveal a paramagnetic behavior, which could be attributed to the dominance exerted by the magnetic moments of the Gd/Dy ions.

Tunable Optical Properties and Relaxor Behavior in Ni/Ba Co-Doped NaNbO3 Ceramics: Pathways Toward Multifunctional Applications

In this study, Ni/Ba co-doped NaNbO3 ceramics (NBNNOx) were synthesized using a solid-state method to explore the effects of Ni2+ and Ba2+ ion substitution on the structural, optical, and dielectric properties of NaNbO3. X-ray diffraction (XRD) confirmed that the ceramics retained an orthorhombic structure, with crystallinity improving as the doping content (x) increased. Significant lattice distortions induced by the Ni/Ba co-doping were observed, which were essential for preserving the perovskite structure. Raman spectroscopy revealed local structural distortions, influencing optical properties and promoting relaxor behavior. Diffuse reflectance measurements revealed a significant decrease in band gap energy from 3.34 eV for undoped NaNbO3 to 1.08 eV at x = 0.15, highlighting the impact of co-doping on band gap tunability. Dielectric measurements indicated relaxor-like behavior at room temperature for x = 0.15, characterized by frequency-dependent anomalies in permittivity and dielectric loss, likely due to ionic disorder and structural distortions. These findings demonstrate the potential of Ni/Ba co-doped NaNbO3 ceramics for lead-free perovskite solar cells and other functional devices, where tunable optical and dielectric properties are highly desirable.

First-principles investigations on the structural and optoelectronic properties of lead-free perovskite Mn:CsSnX3

Nontoxic metal halide perovskites have become a research hotspot in the field of solar cells and other optoelectronic devices. However, low power conversion efficiency owing to their instability limits their wide practical applications. Herein, the structural stability and optoelectronic properties of 12.5% Mn-doped CsSnX3 (X = I, Br, and Cl) perovskite systems were investigated via first-principles computations. The investigations of the formation energy and mechanical parameters indicated that Mn-doping improved the structural stability. As for electronic properties, the band structures of CsSnX3 changed from direct to indirect bandgap after Mn-doping because of the modulation of the crystal field between ions caused by the substitution of Sn ions with Mn ions. The optical properties of the CsSn0.875Mn0.125X3 perovskite were studied, including absorption coefficient, extinction coefficient, reflectivity, and refractive coefficient. The results of this work provide theoretical support for the design of next-generation lead-free and low-toxicity optoelectronic and photovoltaic materials and devices.

Effect of Gd doping on the structural, magnetic and dielectric properties of Y-type hexaferrite BaSrCo2(Fe1-xGdx)11AlO22 ceramics

In this study, the impact of Gd3+ doping on the structural, magnetic and dielectric properties of BaSrCo2(Fe1-xGdx)11AlO22 (x = 0, 0.02, 0.04, 0.06, 0.08, 0.1) ferrite ceramics synthesized by the conventional solid-state reaction method are investigated. XRD results reveal that all the samples crystallize in the R 3‾ m space group. With the increase of Gd content, the formation of M-type phase is effectively inhibited due to Gd3+ ions may change the activation energy of nucleation of the grains and the formation energy of hexaferrite. SEM analysis confirms the presence of hexagonal grains in samples with homogeneous elements distribution. The XPS results verify the coexistence of ferric and ferrous ions in the ceramics. The magnetization and coercivity are suppressed by Gd3+ substitution. The permeability increases firstly and then decreases with the substitution of Gd ions. While the dielectric constant increases with the substitution of Gd. The real and imaginary parts of the dielectric constant in the frequency range of 2–18 GHz change slightly with doping amounts variation, and all the samples exhibit prominent peaks at about 14 GHz due to natural resonance.

Removal of Radioactive Co(II) and Sr(II) using (Co0.5Zn0.5)Fe2O4 Nanoparticles Co-doped with Barium and Antimony

Radioactive pollution poses significant environmental and health risks, including increased cancer rates, genetic mutations, and ecosystem damage, making the removal of radioactive ions from water crucial. Spinel ferrite nanoparticles are promising adsorbents for this purpose owing to their magnetic and adsorption properties. Herein, the novel synthesis of (Co0.5−xZn0.5−xBaxSbx)Fe2O4 nanoparticles (0 ≤ x ≤ 0.1) is reported as an effective solution for adsorbing radioactive Co(II) and Sr(II) ions. Co-doping with Ba and Sb enhances the structural stability, magnetic behavior, and adsorption efficiency of these nanoparticles. X-ray diffraction analysis confirmed sample purity with minimal hematite phase, while Fourier transform infrared spectroscopy verified the spinel structure. Transmission electron microscopy analysis revealed spherical morphology and indicated that increasing x from 0.00 to 0.10 reduced crystallite and grain sizes of nanoparticles from 11.28 to 6.49 nm and 24.47 to 10.88 nm, respectively. Energy-dispersive X-ray spectroscopy confirmed pure elemental compositions and the successful substitution of host ions with dopant ions in the nanoparticles, while X-ray photoelectron spectroscopy analysis provided insights into the chemical oxidation states. Vibrating sample magnetometer results indicated soft ferromagnetic behavior. In adsorption experiments, we examined contact time (0–180 min), pH (2–10), adsorbent dosage (0.04–0.10 g), initial ion concentration (10–250 mg.L−1), and temperature (293–313 K) to determine their effects on adsorption efficiency and optimize conditions for maximum contaminant removal. Nanoparticles with x = 0.06 exhibited the highest ion-removal efficiencies, achieving 88.3% for Co(II) and 96.3% for Sr(II) after contact time of 180 min, with maximum efficiencies observed at pH 8 for Co(II) and pH 6 for Sr(II). Co(II) adsorption followed the Freundlich isotherm, while Sr(II) adsorption adhered to the Temkin model. Kinetics for both ions conformed to the pseudo-second-order model, demonstrating the potential of Ba and Sb co-doped ferrite nanoparticles for efficient radioactive-water purification.

Microwave Absorption and Magnetic Properties of M-Type Hexagonal Ferrite Ba0.95Ca0.05Fe12-xCoxO19 (0 ≤ X ≤ 0.4) at 1-18 GHz.

In order to improve the microwave-absorption performance of barium ferrite and broaden its microwave-absorption band, BaFe12O19, Ba0.95Ca0.05Fe12O19, and Ba0.95Ca0.05Fe12-xCoxO19 (x = 0.1, 0.2, 0.3 and 0.4, respectively) hexaferrites were synthesized by the solid-state reaction method, and the influence of Co ion substitution on the phase composition, microstructure, magnetic properties, and microwave-absorption ability of the ferrites in this system was studied. Introducing minor Co ions (x < 0.2) facilitated sintering and grain growth. At x ≥ 0.2, XRD revealed the emergence of the Co2X phase alongside the BaM phase. Increasing Co ion concentration and the secondary X-phase led to slight reductions in saturation magnetization (69 to 63.5 emu/g) and substantial decline in coercivity (2107.02 to 111.21 Oe), attributed to grain size growth and Co2X's soft magnetic nature. Notably, Co2X incorporation significantly enhanced the microwave absorption and provided a tunable absorption band from the Ku to the C band. For a sample with a thickness of 2.0 mm and a doping level of x = 0.2, a minimum reflection loss of -59.5 dB was achieved at 8.92 GHz, with an effective absorption bandwidth of 3.31 GHz (7.07-10.38 GHz). The simple preparation method and good performance make Ba0.95Ca0.05Fe12-xCoxO19 (x = 0.1, 0.2, 0.3 and 0.4, respectively) hexaferrites promising microwave-absorbing materials.

Exploiting Deep‐Ultraviolet Nonlinear Optical Material Rb2ScB3O6F2 Originated from Congruously Oriented [B3O6] Groups

AbstractThe exploration and research for deep‐ultraviolet (UV) nonlinear optical (NLO) crystals are of great significance for all‐solid‐state lasers. This work is based on the excellent structural [B3O6] units which manipulate the excellent performances of famous commercial NLO crystal β‐BaB2O4 (β‐BBO) to explore new alternatives of deep‐UV NLO materials. A deep‐UV rare‐earth metal borate fluoride Rb2ScB3O6F2 (RSBF) is successfully designed by combining the heterovalent ions substitution strategy, and fluorination strategy. Expectedly, RSBF exhibits an extremely short cutoff edge below 175 nm (189 nm for β‐BBO), and a moderate birefringence of 0.088 at 1064 nm. The shortest phase‐matching (PM) wavelength of RSBF (λPM=182 nm) is shortened by 23 nm compared with β‐BBO (λPM=205 nm) due to the improvements in the chromatic dispersion and cutoff edge, and an experimental frequency‐doubling effect 1.4×KH2PO4 (KDP) further suggests that RSBF can output a deep‐UV harmonic laser. This work provides new sights from the original influencing factors for the rational and purposeful design of deep‐UV NLO materials.

Exploiting Deep-Ultraviolet Nonlinear OpticalMaterial Rb2ScB3O6F2 Originated from Congruously Oriented [B3O6] Groups.

The exploration and research for deep-ultraviolet (UV) nonlinear optical (NLO) crystals are of great significance for all-solid-state lasers. This work is based on the excellent structural [B3O6] units which manipulate the excellent performances of famous commercial NLO crystal β-BaB2O4 (β-BBO) to explore new alternatives of deep-UV NLO materials. A deep-UV rare-earth metal borate fluoride Rb2ScB3O6F2 (RSBF) is successfully designed by combining the heterovalent ions substitution strategy, and fluorination strategy. Expectedly, RSBF exhibits an extremely short cutoff edge below 175 nm (189 nm for β-BBO), and a moderate birefringence of 0.088 at 1064 nm. The shortest phase-matching (PM) wavelength of RSBF (λPM=182 nm) is shortened by 23 nm compared with β-BBO (λPM=205 nm) due to the improvements in the chromatic dispersion and cutoff edge, and an experimental frequency-doubling effect 1.4×KH2PO4 (KDP) further suggests that RSBF can output a deep-UV harmonic laser. This work provides new sights from the original influencing factors for the rational and purposeful design of deep-UV NLO materials.

Biobased Polymers Enabling the Synthesis of Ultralong Silver Nanowires and Other Nanostructures.

Conventional polyol synthesis of silver nanowires has exclusively relied on polyvinylpyrrolidone (PVP), a nonbiodegradable polymer with no viable alternatives. The underlying reaction mechanism remains unclear. Herein, we discovered a new sustainable solution by employing biobased cellulose derivatives, including hydroxyethyl cellulose (HEC), as effective substitutes for PVP. Under mild reaction conditions (125 °C, ambient pressure), HEC facilitates the growth of ultralong silver nanowires (>100 μm) from penta-twinned silver seeds through a four-stage kinetic process. Theoretical calculations further reveal that HEC is physiosorbed onto the silver surfaces, while the presence of bromide ions (Br-) facilitates the evolution of seeds into nanowires. By varying halide ion concentrations and substitution in different cellulose derivatives, we successfully synthesized silver nanostructures with additional intriguing morphologies, including quasi-spherical nanoparticles, bipyramids, and nanocubes. Furthermore, transparent conductive films fabricated from ultralong silver nanowires synthesized with HEC demonstrated superior performance compared to those made with PVP-synthesized nanowires.