Solid Compounds Research Articles

Charge Transfer Interaction Dynamics between 2-Methyl-8-hydroxyquinoline and 2,4-Dinitrophenol: Synthesis, Spectroscopic Characterization, DNA Binding and DFT Studies

A novel charge transfer (CT) complex was formed by combining the electron-acceptor 2,4-dinitrophenol (DNP) with the electron-donor 2-methyl-8-hydroxyquinoline (MHQ). The complex obtained was further characterized using both experimental and theoretical methods. The Benesi-Hildebrand equation can be utilized to determine various spectroscopic physical measurements such as the molar absorptivity (εCT) and formation constant (KCT). The CT complex has a stoichiometry of 1:1. Multiple spectroscopic methods were employed to investigate the resultant solid compound. The existence of charge and proton transfer in the resultant complex was confirmed by FT-IR, 1H NMR, SEM-EDX and powder-XRD studies. An electron absorption spectroscopy examination was done to analyze the complex DNA binding capability. The resulting complex was determined to have an intercalative binding mechanism, with an intrinsic binding constant (Kb) value of 4.2 × 106 M-1. The experimental results were corroborated by performing theoretical calculations using DFT using a CAM-B3LYP/6-31G(d,p) basis set. The geometrical parameters, electrostatic potential maps (MEPs) and Mullikan charges were computed and examined in agreement with the experimental observations. In addition to electron transmission, the stability of the complex is influenced by the presence of a hydrogen bond.

Review of the Literature on the Thermal Stability and Conductivity of Solid Acid Fuel Cells

AbstractThe fuel cell carries the promise of being ecologically beneficial and being one of the renewable energy choices. Solid acids have super‐protonic behavior, allowing them to act as conductors. It can operate at high temperatures. Hydration, on the other hand, can be employed to increase the solid acid and performance. Furthermore, the size of the electrolyte membrane influences the conductivity, stability, and crystal structure of the fuel cell solid acid compounds. Very few studies have been conducted on solid acid fuel cells, which are still being researched in order to make them feasible as well as a trustworthy alternative to clean renewable energy. This review presents an outline of the variables or attributes and current challenges that influence the technical efficacy and performance of the unique super‐protonic conductors for solid acid fuel cells.

Analysis of the electrical conductivity and activation energies of bismuth titanate (Bi4Ti3O12)

In this study, bismuth titanate (Bi4Ti3O12) was synthesized from pure solid compounds and structurally characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The electrical properties were evaluated by measuring the electrical conductivity of Bi4Ti3O12 at various oxygen partial pressures (pO2 = 10−5 and 10−8 atm) and temperatures (450 °C-750 °C). The electrical conductivity behavior was assessed during the heating and cooling processes. The material activation energies were determined based on the heating curve, which displayed Arrhenius-type behavior and activation energy slope changes, which could be attributed to point defects. When the temperature was increased from 450 °C to 750 °C at oxygen partial pressures pO2 = 10−5 atm, the electrical conductivity increased by about 62.9 %, whereas when the temperature decreased from 750 °C to 450 °C, the electrical conductivity was reduced by 35.95 %. The electrical behavior of Bi4Ti3O12 was analyzed by establishing its electrical conductivity and chemical activity under different oxygen partial pressures and heating-cooling conditions can allow the synthesis of materials with attractive characteristics for electronic applications.

A comparative study of discharging and leaching of spent lithium-ion battery recycling

Accelerated production of lithium-ion batteries (LIBs) implies an increase in the raw materials demand, especially for metals like lithium, cobalt, and nickel. Spent LIBs recycling guarantees the regeneration and reincorporation of valuable materials into the manufacturing industry; therefore, recycling methods and techniques must be optimized. In this investigation, alkaline and reductive acid leaching processes were evaluated and compared in order to determine the effect of parameters such as pH, temperature, and reagents concentrations to achieve selective leaching processes. This study demonstrated that strongly alkaline solutions (NaOH) do not ensure selective lithium and aluminum dissolution. Also, a solid compound, LiAl2(OH)6OH(s) can be formed at pH ∼14, negatively affecting the lithium extraction. On the other hand, reductive acid leaching, with acid sulfuric and hydrazine sulfate (H2SO4 + N2H6SO4) solutions resulted in an efficient system, extracting ≥90 % of Ni, Co, and Mn at 40 °C. Hydrazine is essential as a reductant, although it must be added in excess (40 % excess with respect to the Co, Ni, and Mn content) to suppress copper dissolution. Furthermore, this work demonstrated the possibility of processing the entire spent LIBs sample once the discharge and crushing stages were concluded, avoiding physical separation, without affecting the leaching efficiency and contributing to process economy.

Near-infrared luminescence shift in Ni2+-doped double perovskite phosphors

For applications such as near-infrared (NIR) spectroscopy requiring energy-efficient and compact broadband NIR light sources, a variety of Ni2+-doped phosphors emitting in the 1100–2000 nm range has been developed. However, the commercialization of Ni2+-doped NIR phosphors has not yet been achieved, and material exploration is ongoing. To gain insight into the luminescence properties of Ni2+, including emission wavelength and efficiency influenced by compositional and structural variations, Ni2+-doped double-perovskite AELaMgTaO6:Ni2+ (AE = Ba, Sr, or Ca) ceramic samples were synthesized, and their optical properties were examined. Because the energy of the Ni2+ 3d-3d transition is sensitive to structural variations in the local environment around the Ni2+ ions, we investigated the variation in optical properties by indirect ligand field engineering of NiO6 octahedra following the substitution of alkaline earth ions AE2+. The prepared AELaMgTaO6:Ni2+ samples were Ba-Sr or Ba-Ca complete solid solution systems with cubic-to-monoclinic phase transitions. The broad NIR luminescence band at ∼1350–1700 nm was blue-shifted by ∼100 nm, accompanied by Sr2+ or Ca2+ substitution. The local symmetry of the NiO6 octahedra was reduced from Oh to Ci owing to the phase transition, resulting in an enhancement of the NIR luminescence intensity and an increase in the quenching temperature. This study demonstrated that Ni2+ phosphors with the desired optical properties for NIR spectroscopy applications can be designed by controlling the composition ratio of the host compounds and the resultant variation in the local environment of the solid solution compounds.

Simulation, technical-economic evaluation and risk analysis of the purification of different bio-oils obtained by the fast pyrolysis process

Biomass is a natural compound that originates from various forms of organic matter. One way to transform biomass into value-added products is through the fast pyrolysis process, which is a thermochemical process that produces solid, liquid and gaseous compounds. The main product of this process is the bio-oil, found in the liquid phase and containing a wide range of value-added compounds that can be obtained through extraction and distillation. Simulation is an important tool for predicting, modeling and understanding the feasibility of the desired process, along with economic analysis of risks and uncertainties, which are useful techniques for studying the feasibility of projects. In this context, this work aimed to carry out the simulation using the Aspen Plus ® process simulator, the analysis of economic viability and the analysis of risks and uncertainties of the process of separation and purification of bio-oil compounds, derivatives of wood from eucalyptus, eucalyptus residues and sugarcane bagasse. After completing these steps, the project achieved a good result, with desired products being obtained with a considerable degree of purity for commercialization. Economically, all processes were viable, obtaining a good return on investment and a short payback period, despite the high costs involved. Even considering risks and uncertainties, including the variation in the cost of raw materials and production capacity, the investment still returned good results, demonstrating that the project is economically viable even under these circumstances.

Designing electrolytes with high solubility of sulfides/disulfides for high-energy-density and low-cost K-Na/S batteries

Alkaline metal sulfur (AMS) batteries offer a promising solution for grid-level energy storage due to their low cost and long cycle life. However, the formation of solid compounds such as M2S2 and M2S (M = Na, K) during cycling limits their performance. Here we unveil intermediate-temperature K-Na/S batteries utilizing advanced electrolytes that dissolve all polysulfides and sulfides (K2Sx, x = 1–8), significantly enhancing reaction kinetics, specific capacity, and energy density. These batteries achieve near-theoretical capacity (1655 mAh g−1 sulfur) at 75 °C with a 1 M sulfur concentration. At a 4 M sulfur concentration, they deliver 830 mAh g−1 at 2 mA cm−2, retaining 71% capacity after 1000 cycles. This new K-Na/S battery with specific energy of 150-250 Wh kg−1 only employs earth-abundant elements, making it attractive for long-duration energy storage.

Metal Ion Modulated Electron Transfer in Metalloviologen Compounds: Photochromism and Differentiable Amine Detection.

Different types of electron transfers (ETs) underlie the versatile use of various solid viologen-derived compounds, which is still insufficiently understood and difficult to control. Here, we demonstrate an effective strategy for modulating the key ET process in crystalline metalloviologen compounds (MVCs). By adjusting the coordinated transition metal ions bearing different electronic structures (e.g., d5, d7, d10), three MVCs (i.e., Mn-1, Co-2, and Cd-3) with highly consistent coordination environments have been synthesized successfully. Surprisingly, whether the photochromism (energy-induced ET mechanism) or the specific analyte recognition (molecule-induced ET mechanism), compound Cd-3 exhibits obvious photochromic behavior and differential dimethylamine detection. Combined detailed structural analysis with theoretical calculations, such unique ion-dependent properties, were correlated to the fine modulation of the electron density of the bipyridinium cores by metal ions. Additionally, thanks to the delicate recognition of dimethylamine vapor, a convenient test strip Cd-3-PAN was prepared as a sensitive biogenic amine sensor for evaluating the real-time freshness of seafood.

The Formation of a Low-Carbon Steel/Ni-Cr-W Alloy Bimetallic Material via Liquid–Solid Compound Casting with a Laser Assisted Solid Surface

The aim of this study was to develop a new manufacturing process for bimetallic materials by combining laser treatment with traditional casting methods. This process involves laser-treating nickel alloy-grade UNS 6230 plates to create a regular macro-relief on their surface. These treated plates are then placed in a sand mold, and molten non-alloy steel (S235JRG2) is poured into the mold to create bimetallic layered castings. The experimental procedure focuses on optimizing the melt-to-solid phase ratios and pouring temperatures to achieve a uniform microstructure and strong mechanical properties in the bimetals. The produced bimetallic castings are suitable for applications in the oil refining and chemical industries and heavy machinery sector. The quantitative results indicate that the optimized process parameters lead to a high-quality transition zone with minimal defects, characterized by the diffusion of alloying elements from the nickel alloy to the steel. The microstructure, chemical, and phase compositions were evaluated using XRD and SEM with EDS, confirming the formation of a robust metallurgical bond. Key findings include a significant improvement in the hardness and strength of the transition layer, with the optimal pouring temperature being 1600 °C. The resulting bimetallic materials demonstrate an improved performance in demanding industrial environments.

Exploring the influence of deposit mineral composition on biofilm communities in oil and gas systems.

Inside oil and gas pipelines, native microbial communities and different solid compounds typically coexist and form mixed deposits. However, interactions between these deposits (primarily consisting of mineral phases) and microorganisms in oil and gas systems remain poorly understood. Here, we investigated the influence of magnetite (Fe3O4), troilite (FeS), and silica (SiO2) on the microbial diversity, cell viability, biofilm formation, and EPS composition of an oil-recovered multispecies consortium. An oilfield-recovered microbial consortium was grown for 2 weeks in separate bioreactors, each containing 10 g of commercially available magnetite (Fe3O4), troilite (FeS), or silica (SiO2) at 40°C ± 1°C under a gas atmosphere of 20% CO2/80% N2. The microbial population formed in troilite significantly differed from those in silica and magnetite, which exhibited significant similarities. The dominant taxa in troilite was the Dethiosulfovibrio genus, whereas Sulfurospirillum dominated in magnetite and silica. Nevertheless, biofilm formation was lowest on troilite and highest on silica, correlating with the observed cell viability. The dissolution of troilite followed by the liberation of HS- (H2S) and Fe2+ into the test solution, along with its larger particle size compared to silica, likely contributed to the observed results. Confocal laser scanning microscopy revealed that the EPS of the biofilm formed in silica was dominated by eDNA, while those in troilite and magnetite primarily contained polysaccharides. Although the mechanisms of this phenomenon could not be determined, these findings are anticipated to be particularly valuable for enhancing MIC mitigation strategies currently used in oil and gas systems.

Molecular dynamics study on the diffusion of organosulfur compounds in porous solids

Molecular dynamics study on the diffusion of organosulfur compounds in porous solids

Uranium partitioning between apatite and hydrothermal fluids at 150–250 °C

This experimental study is focused on the immobilization of dissolved uranium (U) via its entrapment by apatite at hydrothermal conditions. Experiments on apatite crystallization were conducted in 0.5 M sodium chloride (NaCl) solutions at temperatures of 150, 200, and 250 °C. Uranium was introduced into the system as a solid compound (UO3), which controlled the concentration of dissolved U in the hydrothermal fluids. The results showed that U contents in apatite exceed U concentrations in co-existing fluid by 2–3 orders of magnitude. Apparent Nernst partition coefficients (DU) and exchange coefficient (KU/Ca) were evaluated. Experimentally determined DU values were consistent with DU predicted by the Lattice Strain Model at 200 and 250 °C. The obtained KU/Ca values shows dependence on temperature. The results lay the foundation for further assessment of uranium immobilization in apatite and other minerals at repository conditions.

Impact of solvent dry down, phase change, vehicle pH and slowly reversible keratin binding on skin penetration of cosmetic relevant compounds: II. Solids

We extended a mechanistic, physics-based framework of the dry down process, previously developed for liquids and electrolytes, to solids and coded it into the latest UB/UC/P&G skin permeation model, herein renamed DigiSkin. The framework accounts for the phase change of the permeant from dissolved in a solvent (liquid) to precipitated on the skin surface (solid). The evaporation rate for the solid is reduced due to lower vapor pressure for the solid state versus subcooled liquid. These vapor pressures may differ by two orders of magnitude. The solid may gradually redissolve and penetrate the skin. The framework was tested by simulating the in vitro human skin permeation of the 38 cosmetically relevant solid compounds reported by Hewitt et al., J. Appl. Toxicol. 2019, 1–13. The more detailed handling of the evaporation process greatly improved DigiSkin evaporation predictions (r2 = 0.89). Further, we developed a model reliability prediction score classification using diverse protein reactivity data and identified that 15 of 38 compounds are out of model scope. Dermal delivery predictions for the remaining chemicals have excellent agreement with experimental data. The analysis highlighted the sensitivity of water solubility and equilibrium vapor pressure values on the DigiSkin predictions outcomes influencing agreement with the experimental observations.

Synthesis and radiation damage tolerance of Mo0.75W0.25AlB solid solution for nuclear fusion reactor applications

MAB phases (M = transition metal, A = aluminium (Al), B = boron (B)), a new family of nano-laminated ternary transition metal borides with an excellent combination of functional and structural properties, are currently being investigated as potential radiation shielding materials in nuclear fusion reactors. Here, we report the fabrication of a solid solution MAB phase Mo0.75W0.25AlB (Mo - molybdenum, W - tungsten), in the form of dense and high purity pellets, synthesised for the first time using a reactive hot-pressing method. The shielding and irradiation damage properties of the material were also evaluated. Monte Carlo N-Particle (MCNP) calculations showed that W doping in the MoAlB phase is likely to enhance the shielding capacity against neutrons and gamma rays of different energies. The experimental damage tolerance of Mo0.75W0.25AlB to silicon ion (Si+) irradiation indicated that this solid solution compound has a high resistance to crack formation and other radiation damage effects compared to that of pure MoAlB. Thermal annealing of the amorphous Mo0.75W0.25AlB layer formed by irradiation showed that the damaged structure easily recrystallizes at high temperatures, completely returning to the virgin state. The results show that this solid solution should be considered as a promising candidate material for radiation shielding components.

SHG behavior of the solid isomorphic compounds Ni- and Cu-5,10,15,20- tetraphenylporphyrinate. An experimental and theoretical study

We prepared and investigated the SHG behavior in the solid state of the two isomorphic Nickel and Copper 5,10,15,20-tetraphenylporphyrinate, that crystallize in the same acentric I4¯2d space group. The compounds were synthesized and characterized, and the Second Harmonic Generation (SHG) response of powdered samples was measured employing a 1.907 μm pulsed laser radiation. During laser irradiation, for both compounds, a gradual increase of the intensity of the SH signal was observed until, after a few minutes, it reached a plateau of about fifty times (for the Ni-TPP) or ten times (for the Cu-TPP) the initial value. We attempted to understand the origin of this phenomenon both through experimental analysis and theoretical calculations. Absorption and vibrational spectroscopies, in solution and solid state, combined with powder X-ray diffraction, both before and after irradiation, do not evidence any chemical degradation, phase transition or amorphization process. Theoretical calculations on little fragments of the Ni/Cu-TPP structure simulate appropriately the structural features of the complexes and their initial experimental SHG response. Magnetic balance measurement in the solid state before and after irradiation, in conjunction with DFT/B3LYP optimization of excited spin states and TDDFT calculations, highlight a change in the electronic and/or spin state due to the irradiation of the complexes.

Polymer-based solid/semi-solid electrolytes in lithium ion batteries

Abstract The inception of lithium-ion batteries with liquid electrolytes can be traced back to the early 1980s. Nevertheless, the utilization of liquid electrolytes has many drawbacks, including its susceptibility to combustion, limited energy density, and very brief operational lifespan. Consequently, there is currently a concerted effort to substitute liquid electrolytes with solid compounds. This study investigates the electrochemical and mechanical features of solid/semi-solid electrolytes used in lithium ion batteries (LIBs) as well as their performance relative to conventional liquid electrolytes, with LIBs having unique challenges related to high flammability, electrochemical instability, and low mechanical stability posed by conventional liquid electrolytes versus solid polymer electrolytes (SPEs) which provide greater safety, mechanical stability but lower ionic conductivity than liquid counterparts. SPEs offer better safety but lack sufficient ionic conductivity which limits their potential. In order to overcome these obstacles, the implementation of gel-based and composite solid and semi-solid electrolytes is proposed as a means to improve ionic conductivity, electrochemical stability, and mechanical stability. The study suggests that a focus should be placed on solid composite electrolytes as they possess higher mechanical stability, which contributes to improved safety. Additionally, these electrolytes exhibit enhanced ionic conductivity within the range of 10−4 to 10−2 S/cm, hence enhancing the performance of LIBs.

Synthesis, spectroscopic characterization and biological activities of complexes of light lanthanide ions with 3-hydroxyflavone

New solid compounds of light lanthanide ions with 3-hydroxyflavone were synthesized in good yields (up to 85 %). The resulting complexes have been thoroughly characterized using various analytical and spectral techniques, including elemental analysis, complexometry, thermogravimetry, UV–VIS, FT-IR, 1H NMR, 109AgNPET LDI MS and fluorescence spectroscopy. The molecular formulas of the complexes were determined as follows: Ln(3HF)3, where 3HF-3-hydroxyflavone, Ln = La(III), Pr(III), Nd(III) and Ln(3HF)3·nH2O, where n = 1 for Ln = Ce(III), Sm(III), Eu(III), and n = 2 for Gd(III). Thermogravimetric studies revealed that the water molecules in the hydrated compounds are located in the outer coordination sphere. Based on the spectral data, it was noted that lanthanide ions interacted with the 3OH and 4CO groups of 3-hydroxyflavone. The effect of lanthanide ion chelation on the excited-state intramolecular proton transfer (ESIPT) process and fluorescence emission of 3HF was investigated. It was found that coordination with metal ions can suppress the ESIPT process and enhance the fluorescence emission of 3HF. The synthesized compounds were also screened for their antibacterial activity, free radical scavenging capacity, and interaction with BSA. The results showed that the complexes exhibit higher biological activity compared to the ligand.

Unravelling the emulsifying properties of unfractionated plant powders: From interface to bulk

Crude plant-based by-product powders can stabilise emulsions. Their chemical composition varies substantially depending on both the source plant and the manufacturing process, resulting in different emulsifying properties. This diversity was assessed by studying the emulsifying properties of three chemically different by-products (apple seed cake: protein-rich, apple pomace: non-protein soluble-rich, and liquorice root: mostly water-insoluble) ground into fine and coarse powders. The properties (droplet size, particle anchoring ratio, rheological properties) of the powder-stabilised emulsions were monitored for one month and linked to powder suspensions properties assessed in the presence and absence of solid particles. The interfacial scale was emphasized as the primary location to study the interactions between mixed emulsifiers. The interfacial properties of the powders, and especially the competition between solid particles and soluble compounds, were successfully linked to emulsions properties. Protein-rich powder-stabilised emulsions contained smaller droplets, whose diameter varied slightly with particle size, confirming soluble macromolecules dominance at interfaces. With the soluble powder, particles and soluble macromolecules acted synergistically at both interfacial and bulk scales, indicating mixed interfaces. Particle size determined the properties of the emulsions stabilised with insoluble powder, suggesting interfaces mostly composed of solid particles. Solid particles ensured the gravitational and thermodynamic stability of all powder-stabilised emulsions.

Fluoride-Based Deep Eutectic Solvents with Amide Dual-Hydrogen-Bond Donors.

Developing F--containing electrolytes is crucial for electrochemical and chemical fluorination. However, balancing the F- concentration and electrochemical stability of the electrolytes remains a challenge. In this study, fluoride-based deep eutectic solvents (F-DESs) were obtained by using amide hydrogen-bond donors (HBDs) containing dual N-H bonds. The obtained F-DES, [TMA]F·3.5[1,3-DMU], was prepared by facilely mixing solid compounds of tetramethylammonium fluoride ([TMA]F) and 1,3-dimethylurea (1,3-DMU), resulting in a high F- concentration (2.6 mol dm-3) and a wide electrochemical window (3.1 V) at room temperature. The electrochemical window was much wider than that of [TMA]F·3.5[EG] (EG, ethylene glycol) as another F-DES with an alcohol HBD (1.9 V). Moreover, [TMA]F·3.5[1,3-DMU] exhibited an ionic conductivity that was 2 orders of magnitude higher than that of [TMA]F·3.5[1,3-DMTU] (1,3-DMTU, 1,3-dimethylthiourea) around room temperature because of the bifurcated hydrogen bonds between the dual N-H bonds of 1,3-DMU and one F-. Thus, [TMA]F·3.5[1,3-DMU] was demonstrated to be applicable to electrochemical fluorination.

Elements of Transition-State Theory in Relation to the Thermal Dissociation of Selected Solid Compounds

Elements of Transition-State Theory in Relation to the Thermal Dissociation of Selected Solid Compounds