Journal of Inorganic and Organometallic Polymers and Materials最新文献

Thiourea-based metal chloride complexes are promising candidates for multifunctional material applications. This paper investigates the structural, mechanical, thermal, and optical properties of M^(II)(SC(NH₂)₂)₄Cl₂ compounds (M = Co, Fe, Mn, Cd) through powder X-ray diffraction, thermogravimetric analysis, first-principles calculations, and Monte Carlo simulations. A gradual reduction in crystallinity (from 98.51 to 82.34%) and crystallite size (from 101.95 to 20.21 nm) with increasing metal ionic radius confirms the steric impact on structural order. Mechanical stability is assessed through elastic moduli and Born stability criteria; the cobalt-based complex shows the highest Young’s modulus and fracture toughness (0.115 MPa·m^1/2). All materials exhibit brittle behavior (Pugh’s ratio < 1.75) and low plastic deformation capacity (Poisson’s ratio < 0.5). Monte Carlo simulations corroborate experimental observations on crystal growth, revealing stronger molecular adsorption in the cobalt and iron complexes, consistent with their lower adsorption energies. Thermophysical studies indicate higher Debye temperatures and lower minimum thermal conductivities for the cobalt complex (208 K, 0.44 W/m·K), suggesting enhanced phonon transport. Conversely, the cadmium complex exhibits the highest dielectric constant and intense optical transitions (2–5 eV), favoring optoelectronic applications. Thermal decomposition profiles confirm its suitability as a single-source precursor for CdS via aerosol-assisted chemical vapor deposition, with a final residue of 29.9%. These results highlight the critical role of metal ion selection in tuning the structure–property relationships of thiourea-based complexes for energy conversion and optoelectronic device applications.

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Benzene 1,3,5-tricarboxylic acid metal-organic frameworks (BTC MOFs), a class of exceptional porous materials with multifunctional capabilities and capable nanogeometries, have recently drawn considerable attention from researchers as potential materials for supercapacitor electrodes. This study introduces a novel Ni-MOF/PANI/GO ternary nanocomposite synthesized via a cost-effective chemical oxidative polymerization method. Graphene oxide (GO) was synthesized using a modified Hummers’ method. A nickel Metal organic framework (Ni-MOFs) was synthesized by a Hydrothermal Method and Polyaniline (PANI) was synthesized by a chemical oxidative polymerization method to study the effect of GO and PANI on the electrochemical properties of Ni-MOF. The structural characterization and morphology of the developed materials were determined by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, UV-Vis spectroscopy, and PL spectroscopy. The grown structure of the ternary nanocomposite with an average crystallite size of 13.767 nm was confirmed by XRD analysis. The different bonds and transmittance peaks were analyzed using FTIR. The D and G bands were analyzed using Raman spectroscopy. An optical band gap (E_g) ~ 4.02 eV was confirmed by UV-Vis and PL spectra. Electrochemical characterization was performed using CV, GCD and EIS analysis in 3 M KOH solution. CV revealed that ternary composite showed maximum specific capacitance of 206 Fg⁻¹ at 1 mVs⁻¹ in 3 M KOH with charge retention of ca. 81.5% after 5000 charge-discharge cycles. This study aimed to synthesize a novel Ni-MOF/PANI/GO ternary nanocomposite and evaluate its electrochemical properties in supercapacitor applications.

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Ferrocenyl Lawesson’s reagent (FcLR) or 2,4-diferrocenyl-1,3- dithiadiphosphetane 2,4-disulfide, which acts as a thionation reagent, is a groundbreaking organometallic compound that has been widely used in numerous fields, particularly in the architecture of novel organometallic compounds. Ferrocene (Fc) attached to a phosphorus-sulfur bond in FcLR is crucial for engineering these complexes. In other words, compared to traditional Lawesson’s reagent (LR) ligands, FcLR demonstrates superior reactivity and greater synthetic versatility, taking advantage of the exceptional properties of phosphorus and sulfur, while the distinctive characteristics of Fc can provide new opportunities in organometallic chemistry and lead to the creation of innovative Fc-containing structures. Here, we reviewed applications of FcLR in the synthesis of its salts, heterocycles, macrocycles, zwitterions, and metal complexes, as well as its utilization in thionation reactions. The categorization presented in this review is based on the reaction products. Finally, other special applications of FcLR and its derivatives are discussed, including their usage in electrochromic polymers, metallopolymers, biosensors, anti-microorganism agents, and dye-sensitized solar cells.

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Today, prioritising the design of a highly active and efficient bifunctional electrocatalyst for water splitting is essential to meet global energy demands. In this study, two acylpyrazolone ligands (HPMBP and HPMTP) were used to form copper complexes {Cu(1) and Cu(2)}. Various analytical techniques and spectroscopic methods have been employed to determine the coordination mode and elucidate the structure and properties of the complexes. Theoretical studies were performed using DFT with the PBE/DNP basis set for calculations on the ligand atoms and their copper complexes. Spectroscopic data showed that the acylpyrazolone ligand acted as an anionic chelating bidentate ligand in copper complexes through the O,O pattern of hydroxyl (C-O-Cu) and carbonyl (C = O-Cu) groups. The geometry of the complexes is assigned as paramagnetic, elongated octahedral around the Cu(II) ion. The DFT study provides a comparative analysis of the reactivity and stability of the synthesised complexes, indicated by their HOMO-LUMO energy gaps, global reactivity, and Fukui descriptors. The high HOMO energy (− 5.754 eV), lower LUMO energy (− 5.510 eV), and high Fukui descriptors were observed for Cu(2) compared to Cu(1), which has a low HOMO energy of -5.690 eV and a high LUMO energy of − 5.520 eV. The complexes were screened for their electrocatalytic activity. Cu(2) has shown a low overpotential of 300 mV@10 mAcm^− 2, a Tafel slope of 50 mV/dec, and an Rct of 2 Ω with excellent stability compared to Cu(1). Investigations of the mechanism revealed that the sulphate and pyrazolone groups participate in the formation of the O–O bond, thus enhancing the catalytic activity of the complexes.

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This study explores the stability of pristine and carbon doped B₂₄N₂₄ nanocages (B₂₄CN₂₃ and B₂₃CN₂₄). The electronic properties and adsorption behavior of hydroxyurea were investigated using density functional theory (DFT). Carbon doping was found to influence the formation energy, with the trend B₂₄CN₂₃ > B₂₄N₂₄ > B₂₃CN₂₄, indicating enhanced stability. Adsorption studies with hydroxyurea (HU) revealed strong O⋅⋅⋅B interactions in A configurations, yielding the most stable adsorption energies and favorable thermodynamic parameters. Carbon doped nanocages exhibited enhanced electronic properties, with reduced energy gaps and modified electrostatic potential maps. Among all configurations studied, the most stable adsorption of hydroxyurea (HU) was observed on the B₂₄CN₂₃ nanocage with an adsorption energy of − 15.31 kcal/mol, while the B₂₄N₂₄ and B₂₃CN₂₄ nanocages showed adsorption energies of − 14.57 kcal/mol and − 12.35 kcal/mol, respectively. The band gap of the pristine B₂₄N₂₄ was 6.56 eV, which decreased to 6.27 eV upon HU adsorption, while B₂₄CN₂₃ and B₂₃CN₂₄ exhibited greater reductions to 5.55 eV and 3.49 eV, respectively. The study highlights the potential of B₂₄CN₂₃ nanocages for controlled HU adsorption and release, supported by favorable thermodynamics and electronic reactivity. These findings provide valuable insights for the application of B₂₄N₂₄ based nanostructures in drug delivery systems.

The clean and environmentally friendly characteristics of photovoltaic solar panel research have long been a source of fascination. A promising option for solar absorber material for ultrathin film solar cells is the triple chalcostibite CuSbS₂ (Copper Antimony Sulfide) system, It has earth-abundant components, affordable prices, vacuum-free production techniques, and an exceptionally high light absorption coefficient. However, the efficiency of a typical CuSbS₂/CdS heterojunction solar panel is extremely low because of the Schottky barrier that forms at the back contact and the significant recombination of carriers at the CdS/CuSbS₂ interface. In this article, SnS₂ (tin disulfide) is suggested as a substitute for the CdS layer in CuSbS₂-based TFSCs (Thin Film Solar Cells). SnS₂, CuSbS₂, and V₂O₅ have been used as ETL (Electron Transport Layer), absorber layer, and BSF (Back Surface Field) layer, respectively. A new n-p-p + heterojunction solar cell based on Al/FTO/SnS₂/CuSbS₂/Ni has been designed and simulated using the SCAPS-1D photovoltaic cell simulator. It has been investigated how integrating the V₂O₅ BSF layer affects the photovoltaic performances of the CuSbS₂-based heterojunction solar cell, about the back-contact recombination of carriers, and the built-in potential. Furthermore, a systematic study has examined the effects of several device characteristics, including operating temperature, shunt and series resistances, back-contact metalwork function, carrier concentration, and layer thickness. The outcomes are examined in connection with the device’s photovoltaic characteristics to maximize the suggested solar cell’s efficiency. At high temperatures, the improved CuSbS₂-based solar cell exhibits good performance stability and a maximum efficiency of 31.09%, V_OC = 1.39 V, J_SC = 25.09 mA/cm², FF = 88.54%. Additionally, a Random Forest Machine Learning algorithm predicts the optimum PCE (Power Conversion Efficiency) using semiconductor parameters. The model quantifies each parameter’s importance using SHAP (Shapley Additive Explanations) values, revealing their contributions. The model predicts performance accurately and provides precise results with a mean correlation coefficient (R²) of 0.84. This study highlights CuSbS₂-based potential as a viable material for sustainable solar cells.

Plasmonic nanoparticle-embedded semiconductor nanostructures offer significant potential in catalysis and sensing applications. In this study, we fabricated highly hierarchical silicon nanowires (SiNWs) via metal-assisted chemical etching, followed by electroless silver deposition to obtain Ag-functionalized silicon nanowires (Ag@SiNW). As-formed nanowires exhibited well-organized, vertically grown nanowires with an average diameter of ~ 49 nm. Post-deposition analysis confirmed the effective coverage of silver nanoarrays both on top and side walls of nanowires. The photocatalytic performance of Ag@SiNW has been systematically investigated as a function of silver deposition duration. It was observed that the photocatalytic efficiency initially increased with decreasing immersion time, reaching a maximum at 5 s and then declined with shorter durations. The maximum degradation efficiency of 99% for methylene blue was achieved after 140 min of light exposure under optimal conditions. Additionally, Ag@SiNW was evaluated as SERS-based chemosensors for tracking methylene blue. The SERS enhancement was found to be tunable by adjusting the silver deposition time, with the highest enhancement observed at 10 s. Ag@SiNW sensors were explored to track the photocatalytic degradation pathway of methylene blue using SERS. The kinetic coefficient of 0.0131 was determined, comparable to values obtained from UV-visible methods. Overall, Ag@SiNW substrates demonstrated versatile functionality in both photocatalysis and optical sensing, highlighting their potential in environmental remediation applications.

This study investigates the photovoltaic (PV) performance of three environmentally friendly double perovskite materials (DPMs) Cs₂SnBr₆, Cs₂SnI₆, and Cs₂PdBr₆ for application in lead-free perovskite solar cells (PSCs). Simulations were conducted using SCAPS-1D software, with TiO₂ as the electron transport layer (ETL) and CuI as the hole transport layer (HTL), configured in the device structure: (FTO/TiO₂/Absorber/CuI/Au). Among the three configurations, Device 1 (Cs₂SnBr₆ based) demonstrated superior performance, achieving power conversion efficiency (PCE) of 31.06%, open-circuit voltage (V_OC) of 1.2641 V, short-circuit current density (J_SC) 33.001 mA.cm^-2, and fill factor (FF) of 74.45%. Device 2 (Cs₂SnI₆ based) and Device 3 (Cs₂PdBr₆ based) achieved PCEs of 30.39% and 27.18%, respectively. Critical factors influencing device performance, including active layer thickness, interfacial defects (IDD), defect density (N_t) vs. thickness, temperature variation (T in K), and series (R_S) and shunt resistances (R_Sh) were thoroughly analyzed. In addition, J–V characteristics and external quantum efficiency (EQE) spectra were evaluated to optimize and validate device efficiency. The findings identify Cs₂SnBr₆ as a promising lead-free DPM, offering an excellent balance between photovoltaic performance and environmental sustainability. This study also establishes a comprehensive simulation framework for the selection and optimization of Cs-based lead-free DPMs, uniquely providing a side-by-side comparison of multiple absorber materials under identical device configurations, an approach that has been largely overlooked in earlier works. These insights contribute meaningfully toward the design of stable and efficient next-generation PSCs.

The growing demand for multifunctional materials in electronics, biomedical devices, and packaging has directed increasing attention toward polymer-based nanocomposites. In this work, a fluorine-containing methacrylate derivative (PTFBMA) was synthesized and blended with poly(vinyl alcohol) (PVA) biopolymer to produce biogenic silver nanoparticles (AgNPs)-containing nanocomposite structures. Trifluoromethyl group and ester chains containing fluorine atoms have the potential to provide high thermal stability, hydrophobic surface properties, and microbial interaction control to the polymer matrix. At the same time, AgNPs obtained by green synthesis were integrated into the nanocomposites to increase surface and electrical performance. As a result of structural characterizations, the transition from monomer to polymer was confirmed by FTIR and NMR analyses; SEM images showed that AgNPs were dispersed and embedded in the matrix, and EDX analyses confirmed an Ag content of up to 23.4%. XRD data showed distinct diffraction peaks belonging to AgNPs at 38.1°, 44.3°, and 64.4° angles. In TGA analysis, it was determined that pure PTFBMA started to decompose at 360 °C, and this temperature increased to 390 °C with 7% AgNPs incorporated. DSC data showed that the glass transition temperature ranged from 85 °C to 101 °C. In surface contact angle measurements, the increase in the water angle from 53.75° to 70.07° with AgNPs incorporation showed that the surface became more hydrophobic. In dielectric analysis, the AC conductivity value at 1 MHz increased to 7.7 × 10^− 6 S/m, the impedance decreased from 3 × 10⁶ ohm to 10⁴ ohm, and the ε′ value was measured as 7.63 in the 7% AgNPs incorporation sample. In addition, the sample containing 5% AgNPs stood out as the most effective structure in biological tests, with an inhibition zone of 11.66 mm on C. albicans. The data gathered shows that the nanocomposites produced can be used in food and medical packaging, antimicrobial, flexible electronic devices, and coating areas.

Researchers are now paying close attention to nanostructured metal vanadates because of their exceptional capabilities in energy conversion, electronic devices, catalysis and storage. The Mo₄V₆O₂₅ nanostructures was prepared via easy wet chemical method. The prepared Mo₄V₆O₂₅ was examined using a variety of analytical and spectral methods. Because of their abundance, relative affordability, and multiple oxidation states, molybdenum and vanadium may generate a wide range of redox reactions that are advantageous for electrochemical function. The developed Mo₄V₆O₂₅ nanostructures can also be utilized as efficient material for supercapacitors (SCs) because of their superior features and easy passage of ions. They demonstrated notable efficiency with significant specific capacity (C_s) of 203 C/g at 1 A/g. Additionally, it shows good cyclic stability and coulombic efficiency (89.5% and 83.5 even after 10,000 cycles at 1 A/g). The nanoflakes-like structure of Mo₄V₆O₂₅ is the best option for use in SCs attributable to its significant high-rate capability as well as cycle stability. After assembling with activated carbon (AC) to form a Mo₄V₆O₂₅//AC device, the energy density (ED) of this Mo₄V₆O₂₅//AC device is 56.9 Wh/kg at a power density (PD) of 1125 W/kg, and remains at a 15 Wh/kg at a power density of 4500 W/kg. The findings suggest that Mo₄V₆O₂₅ nanostructures are excellent options for high-efficiency energy storage systems.