Search Results (1,440)

The removal of high-concentration m-cresol from industrial wastewater remains a significant challenge due to its toxicity and persistence. In this study, a commercially available functionalized resin with a high BET surface area (1439 m² g⁻¹) and hierarchical pore structure was employed for the adsorption of pure m-cresol at an initial concentration of 20 g L⁻¹, representative of coal-based industrial effluents. Comprehensive characterization confirmed the presence of oxygen-rich functional groups, amorphous polymeric structure, and uniform surface morphology conducive to adsorption. Batch experiments were conducted to evaluate the effects of resin dosage, contact time, temperature, and equilibrium concentration. Under optimized conditions (0.15 g resin, 60 °C), a maximum adsorption capacity of 556.3 mg g⁻¹ and removal efficiency of 71% were achieved. Kinetic analysis revealed that the pseudo-second-order model best described the adsorption process (R² > 0.99). Isotherm data fit the Langmuir model most closely (R² = 0.9953), yielding a monolayer capacity of 833.3 mg g⁻¹. Thermodynamic analysis showed that adsorption was spontaneous (ΔG° < 0), endothermic (ΔH° = 7.553 kJ mol⁻¹), and accompanied by increased entropy (ΔS° = 29.90 J mol⁻¹ K⁻¹). The good agreement with the PSO model is indicative of chemisorption, as supported by other lines of evidence, including thermodynamic parameters (e.g., positive ΔH° and ΔS°), surface functional group characteristics, and molecular interactions. The adsorption mechanism was elucidated through comprehensive modeling of adsorption kinetics, isotherms, and thermodynamics, combined with detailed physicochemical characterization of the resin prior to adsorption, reinforcing the mechanistic understanding of m-cresol–resin interactions. Full article

Macrocyclic organic nanostructures have emerged as crucial components of functional supramolecular materials owing to their unique structural and chemical features, such as their distinctive “infinite” cyclic topology and tunable topology-dependent properties, attracting significant recent attention. However, the controlled synthesis of macrocyclic compounds with well-defined compositions and geometries remains a formidable challenge. On-surface synthesis, capable of constructing nanostructures with atomic precision on various substrates, has become a frontier technique for exploring novel macrocyclic architectures. This review summarizes the recent advances in the on-surface synthesis of macrocycles. It focuses on analyzing the synthetic mechanisms and conformational characterization of macrocycles formed through diverse bonding interactions, including both covalent and non-covalent linkages. This review elucidates the intricate interplay between the thermodynamic and kinetic factors governing macrocyclic structure formation across these bonding types and clarifies the critical influence of the reaction temperature and external conditions on the cyclization efficiency. Ultimately, this study offers design strategies for the precise on-surface synthesis of larger and more flexible macrocyclic compounds. Full article

The current work is established with the object of modifying the source of Fenton system and substituting iron source as a catalyst with magnetite/potato peels composite material (POT400-M) to be an innovative solar photocatalyst. The structural and morphological characteristics of the material are assessed through X-ray diffraction (XRD) and scanning electron microscopy (SEM). The technique is applied to treat oil spills that pollute seawater. The effectiveness of the operating parameters is studied, and numerical optimization is applied to optimize the most influential parameters on the system, including POT400-M catalyst (47 mg/L) and hydrogen peroxide reagent (372 mg/L) at pH 5.0, to maximize oil removal, reaching 93%. Also, the aqueous solution and wastewater temperature on the oxidation reaction is evaluated and the reaction exhibited an exothermic nature. Kinetic modeling is evaluated, and the reaction is found to follow the second-order kinetic model. Thermodynamic examination of the data exhibits negative enthalpy (∆H′) values, confirming that the reaction is exothermic, and the system is verified to be able to perform at the minimal activation energy barrier (−51.34 kJ/mol). Full article

Sanicro 25 (X7NiCrWCuCoNb25-23-3-3-2) steel is specifically designed for use in superheater components within the latest generation of conventional power plants. These power plants operate under conditions often referred to as super-ultra-supercritical, with steam parameters that can reach up to 30 MPa and temperatures of 653 °C for fresh steam and 672 °C for reheated steam. While last-generation supercritical power plants still rely on fossil fuels, they represent a significant step forward in more sustainable energy production. The most sophisticated facilities of this kind can achieve thermodynamic efficiencies exceeding 47%. This study aimed to conduct a detailed analysis of the initial precipitation processes occurring in Sanicro 25 steel within the temperature range of 700–900 °C. The temperature of 700 °C corresponds to the operational conditions of this material, particularly in secondary steam superheaters in thermal power plants that operate under ultra-supercritical parameters. Understanding precipitation processes is crucial for optimizing mechanical performance, particularly in terms of long-term strength and creep resistance. To accurately assess the microstructural changes that occur during the early stages of service, a digital twin approach was employed, which included CALPHAD simulations and experimental heat treatments. Experimental annealing tests were conducted in air within the temperature range of 700–900 °C. Precipitation behavior was simulated using the Thermo-Calc 2025a with Dictra software package. The results from Prisma simulations correlated well with the experimental data related to the kinetics of phase transformations; however, it was noted that the predicted sizes of the precipitates were generally smaller than those observed in experiments. Additionally, computational limitations were encountered during some simulations due to the complexity arising from the numerous alloying elements present in Sanicro 25 steel. The microstructural evolution was investigated using various methods, including light microscopy (LM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Full article

: This study reports the development of a sustainable biocatalyst system for free fatty acid (FFA) production from cocoa bean shell (CBS) oil using Burkholderia cepacia lipase (BCL). CBS was explored as both a support material and a reaction substrate. Six immobilized systems were prepared using organic (CBS), inorganic (silica), and hybrid (CBS–silica) supports via physical adsorption or covalent binding. Among them, the covalently immobilized enzyme on CBS (ORG-CB) showed the most balanced performance, achieving a catalytic efficiency (Ke) of 0.063 mM⁻¹·min⁻¹ (18.6% of the free enzyme), broad pH–temperature tolerance, and over 50% activity retention after eight reuse cycles. Thermodynamic analysis confirmed enhanced thermal resistance for ORG-CB (Ed = 32.3 kJ mol⁻¹; ΔH‡ = 29.7 kJ mol⁻¹), while kinetic evaluation revealed that its thermal deactivation occurred faster than for the free enzyme under prolonged heating. In application trials, ORG-CB reached 60.1% FFA conversion from CBS oil, outperforming the free enzyme (49.9%). These findings validate CBS as a dual-function material for enzyme immobilization and valorization of agro-industrial waste. The results also reinforce the impact of immobilization chemistry and support composition on the operational and thermal performance of biocatalysts, contributing to the advancement of green chemistry strategies in enzyme-based processing. Full article

This study investigates two novel algal biosorbents (Ulothrix sp. and Spirogyra sp.) from Djelfa, Algeria, for methylene blue (MB) removal from aqueous solutions. A comprehensive characterization, including scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM–EDS), Brunauer–Emmett–Teller (BET) analysis, porosity measurements, and Fourier-transform infrared spectroscopy (FTIR), revealed distinct physicochemical properties. Ulothrix exhibited a surface area of 5.35 m²/g with an average pore diameter of 32.77 nm, whereas Spirogyra showed values of 3.47 m²/g and 20.97 nm for the surface area and average pore diameter, respectively. Despite their modest surface areas, both algae demonstrated effective adsorption capacities (6.94 mg/g for Spirogyra vs. 6.38 mg/g for Ulothrix), with optimal doses of 0.01 g and 0.08 g (for 50 mL of MB solution), respectively. Kinetic analysis confirmed pseudo-second-order adsorption (R² > 0.97), indicating chemisorption dominance. Isotherm data best fit the Sips model (R² = 0.94), suggesting heterogeneous monolayer formation. Thermodynamic studies revealed an endothermic (ΔH° > 0), spontaneous (ΔG° < 0), yet favorable adsorption process, highlighting the potential of these naturally abundant algae as sustainable biosorbents for dye wastewater treatment. Full article

Excessive phosphate from agriculture and industry has led to widespread eutrophication, posing a serious environmental threat. To address this issue, metal-modified biochars have emerged as promising adsorbents due to their high affinity for phosphate ions. This study investigates the application of two magnesium-modified biochar hydrogels denoted as magnesium–bamboo biochar hydrogel (Mg-BBH) and magnesium–pulp biochar hydrogel (Mg-PBH) for phosphate recovery from aqueous solutions, with an additional aim as slow-release fertilizers. The adsorbents were synthesized by impregnating Mg-modified biochars into sodium-alginate-based hydrogel. The influence of initial phosphate concentration, contact time, and temperature were investigated to determine optimal adsorption conditions. Both adsorbents exhibited excellent adsorption performance, with maximum capacities of 309.96 mg PO₄/g (Mg-BBH) and 234.69 mg PO₄/g (Mg-PBH). Moreover, the adsorption performance of the adsorbents was greatly influenced by the magnesium content. The adsorption process followed the Temkin isotherm and pseudo-second-order kinetics, suggesting that the adsorption energy decreases proportionally with surface coverage and the phosphate uptake was governed by chemisorption. Thermodynamic study confirmed the process was spontaneous and endothermic at 40 °C. A slow-release study further demonstrated a great release of phosphate in soil over time. These findings highlight the dual functionality of Mg-BBH and Mg-PBH as effective materials for both phosphate recovery and controlled nutrient delivery, contributing to sustainable phosphate management. Full article

Stainless steel dust (SSD) is a by-product generated during the smelting process of stainless steel, which is rich in valuable metals such as Fe, Cr, Ni, and Mn. To optimize the carbothermic reduction process of SSD, this study first conducted the thermodynamic analysis of the carbothermic reduction of SSD and then employed walnut shell biochar as a reductant with non-isothermal thermogravimetric analysis with linear heating rates of 5 °C/min, 10 °C/min, 15 °C/min, and 20 °C/min. The activation energies of the carbothermic reduction reactions were calculated using the FWO method, KAS method, and Friedman method, respectively. Subsequently, the corresponding kinetic models were fitted and matched using the Málek method. The results indicate that before 600 °C, the direct reduction of SSD by carbon plays a dominant role. As the temperature increases, the indirect reduction becomes the main reduction reaction for SSD due to the generation of CO. The activation energies calculated by the Flynn–Wall–Ozawa (FWO) method, Kissinger–Akahira–Sunose (KAS) method, and Friedman method are 412.120 kJ/mol, 416.930 kJ/mol, and 411.778 kJ/mol, respectively, showing close values and a general trend of increasing activation energy as the conversion rate increased from 10% to 90%. Moreover, the reduction reaction is staged. In the conversion range of 10% to 50%, the carbothermic reduction reaction conforms to the shrinking core model within phase boundary reactions, coded as R1/4. In the conversion range of 50% to 60%, it conforms to the shrinking core model within phase boundary reactions, coded as R1/2; in the conversion range of 60% to 90%, the carbothermic reduction reaction follows the second-order chemical reaction model, coded as F2. Full article

Aimed at developing an economical and efficient biosorbent for the adsorption and separation of rare earth ions, this study employed Spirulina dry powder biomass as a biosorbent to investigate its removal performance for Pr³⁺ in aqueous solutions. Experimental results demonstrated that under optimized conditions (pH = 5, adsorbent dosage = 2.0 g/L, initial Pr³⁺ concentration = 100 mg/L, and adsorption time = 60 min), the removal efficiency of Pr³⁺ reached 79.0%. FT-IR and XPS characterization confirmed the participation of various functional groups on the Spirulina surface in the adsorption process. When 0.1 mol/L HNO₃ was used as the desorption agent, the desorption rate of Pr³⁺ from Spirulina reached 91.7%, demonstrating excellent regeneration performance. At different temperatures (298–318 K), the adsorption data were fitted using Langmuir, Freundlich, Dubinin–Radushkevich, and Redlich–Peterson models. Among them, the Langmuir model (R² ranged from 0.993 to 0.999) provided the best fit, and the adsorption capacity of Spirulina for Pr³⁺ was in the range of 51.10 to 55.31 mg/g. Kinetic studies revealed that the pseudo-second-order model (R² = 0.999) best described the adsorption process, with a rate constant of 0.054 g/(mg·min) (R² was 0.999) at an initial Pr³⁺ concentration of 300 mg/L, indicating chemisorption-controlled behavior. Thermodynamic parameter analysis showed that within the experimental temperature range, ΔG⁰ < 0 and ΔS⁰ > 0, confirming that the adsorption process was spontaneous and endothermic. This study provides a novel technical approach for the green recovery of rare earth elements and highlights the potential of Spirulina biomass in rare earth resource recycling. Full article

Vacuum degassing (VD) is a critical refining step in electric arc furnace (EAF) steelmaking for producing clean steel with reduced nitrogen and hydrogen content. This study develops an Effective Equilibrium Reaction Zone (EERZ) model focused on denitrogenation (de-N) by simulating interfacial reactions at the bubble–steel interface (Z1). The model incorporates key process parameters such as argon flow rate, vacuum pressure, and initial nitrogen and sulfur concentrations. A robust empirical correlation was established between de-N efficiency and the mass of Z1, reducing prediction time from a day to under a minute. Additionally, the model was further improved by incorporating a dynamic surface exposure zone (Z_eye) to account for transient ladle eye effects on nitrogen removal under deep vacuum (<10 torr), validated using synchronized plant trials and Python-based video analysis. The integrated approach—combining thermodynamic-kinetic modeling, plant validation, and image-based diagnostics—provides a robust framework for optimizing VD control and enhancing nitrogen removal control in EAF-based steelmaking. Full article

A facile method was adopted to fabricate β-C₃N₄, and it was then doped with manganese and tellurium to obtain novel 10%MnTeO₃@β-C₃N₄ (10%MnTe@β) and 20%MnTeO₃@β-C₃N₄ (20%MnTe@β) nanohybrids. The β-C₃N₄, 10%MnTe@β, and 20%MnTe@β showed surface areas of 85.86, 97.40, and 109.54 m² g⁻¹, respectively. Using ciprofloxacin (CIP) as a pollutant example, 10%MnTe@β and 20%MnTe@β attained equilibrium at 60 and 45 min with q_t values of 48.88 and 77.41 mg g⁻¹, respectively, and both performed better at pH = 6.0. The kinetic studies revealed a better agreement with the pseudo-second-order model for CIP sorption on 10%MnTe@β and 20%MnTe@β, indicating that the sorption was controlled by a liquid film mechanism, which suggests a high affinity of CIP toward 10%MnTe@β and 20%MnTe@β. The sorption equilibria outputs indicated better alignment with the Freundlich and Langmuir models for CIP removal by 10%MnTe@β and 20%MnTe@β, respectively. The thermodynamic analysis revealed that CIP removal by 10%MnTe@β and 20%MnTe@β was exothermic, which turned more spontaneous as the temperature decreased. Applying 20%MnTe@β as the best sorbent to groundwater and seawater spiked with CIP resulted in average efficiencies of 94.8% and 91.08%, respectively. The 20%MnTe@β regeneration–reusability average efficiency was 95.14% within four cycles, which might nominate 20%MnTe@β as an efficient and economically viable sorbent for remediating CIP-contaminated water. Full article

TiVCr-based alloys are well-explored body-centered cubic (BCC) materials for hydrogen storage applications that can potentially store higher amounts of hydrogen at moderate temperatures. The challenge remains in optimizing the alloy-hydrogen stability, and several transition elements have been found to support the reduction in the hydride stability. In this study, Ni and Nb transition elements were incorporated into the TiVCr alloy system to thoroughly understand their influence on the (de)hydrogenation kinetics and thermodynamic properties. Three different compositions, (TiVCr)₉₅Ni₅, (TiVCr)₉₀ Ni₁₀, and (TiVCr)₉₅Ni₅Nb₅, were prepared via arc melting. The as-prepared samples showed the formation of a dual-phase BCC solid solution and secondary phase precipitates. The samples were characterized using hydrogen sorption studies. Among the studied compositions, (TiVCr)₉₀Ni₁₀ exhibited the highest hydrogen absorption capacity of 3 wt%, whereas both (TiVCr)₉₅Ni₅ and (TiVCr)₉₀Ni₅Nb₅ absorbed up to 2.5 wt% hydrogen. The kinetics of (de)hydrogenation were modeled using the JMAK and 3D Jander diffusion models. The kinetics results showed that the presence of Ni improved hydrogen adsorption at the interface level, whereas Nb substitution enhanced diffusion and hydrogen release at room temperature. Thus, the addition of Ni and Nb to Ti-V-Cr-based high-entropy alloys significantly improved the hydrogen absorption and desorption properties at room temperature for gas-phase hydrogen storage. Full article

The discharge of synthetic dyes in industrial wastewaters poses a serious environmental threat as they are difficult to degrade naturally and are harmful to aquatic organisms. This study aimed to evaluate the feasibility of using clean untreated rice husk (CRH) as a sustainable and low-cost adsorbent for the removal of methylene blue (MB) from synthetic wastewater. This approach effectively avoids the energy-intensive grinding process by directly using whole unprocessed rice husk, highlighting its potential as a sustainable and cost-effective alternative to activated carbon. A series of batch adsorption experiments were conducted to evaluate the effects of key operating parameters such as initial dye concentration, contact time, pH, ionic strength, and temperature on the adsorption performance. Adsorption kinetics, isotherm models, and thermodynamic analysis were applied to elucidate the adsorption mechanism and behavior. The results showed that the maximum adsorption capacity of CRH for MB was 5.72 mg/g. The adsorption capacity was stable and efficient between pH 4 and 10, and reached the highest value at pH 12. The presence of sodium ions (Na⁺) and calcium ions (Ca²⁺) inhibited the adsorption efficiency, with calcium ions having a more significant effect. Kinetic analysis confirmed that the adsorption process mainly followed a pseudo-second-order model, suggesting the involvement of a chemisorption mechanism; notably, in the presence of ions, the Elovich model provided better predictions of the data. Thermodynamic evaluation showed that the adsorption was endothermic (ΔH° > 0) and spontaneous (ΔG° < 0), accompanied by an increase in the disorder of the solid–liquid interface (ΔS° > 0). The calculated activation energy (Ea) was 17.42 kJ/mol, further supporting the involvement of chemisorption. The equilibrium adsorption data were well matched to the Langmuir model at high concentrations (monolayer adsorption), while they were accurately described by the Freundlich model at lower concentrations (surface heterogeneity). The dimensionless separation factor (RL) confirmed that the adsorption process was favorable at all initial MB concentrations. The results of this study provide insights into the application of agricultural waste in environmental remediation and highlight the potential of untreated whole rice husk as a sustainable and economically viable alternative to activated carbon, which can help promote resource recovery and pollution control. Full article

The design of emulsions at the nanoscale is a significant application of nanotechnology. For spherical droplets and a given volume of dispersed phase, the nanometre size of droplets inversely increases the total area, $A={\displaystyle \frac{3V}{r}}$, allowing greater contact with organic and inorganic materials during application. In topical applications, not only is cell contact increased, but also permeability in the cell membrane. Nanoemulsions typically achieve kinetic stability rather than thermodynamic stability, so their commercial application requires reasonable resistance to flocculation and coalescence, which can be affected by temperature changes. Therefore, their thermoresponsive characterisation becomes relevant. In this work, we analyse this response in an O/W nanoemulsion of Palmarosa for antibacterial purposes that has already shown stability for one year at controlled room temperature. We now study hysteresis processes and the behaviour of the statistical distribution in droplet size by Dynamic Light Scattering, obtaining remarkable stability under temperature changes up to 50 °C. This includes a maintained chemical composition observed using Fourier Transform Infrared Spectroscopy and the preservation of antibacterial properties analysed through optical density tests on cultures and the Spread-Plate technique for bacteria colony counting. We obtain practically closed hysteresis curves for some tracers of droplet size distributions through controlled thermal cycles between 10 °C and 50 °C, exhibiting a non-linear behaviour in their distribution. In general, the results show notable physical, chemical, and antibacterial stability, suitable for commercial applications. Full article

Background/Objectives: Tegoprazan (TPZ) is a potassium-competitive acid blocker (P-CAB) used to treat conditions such as gastroesophageal reflux disease, peptic ulcer, and Helicobacter pylori infection. It exists in three solid forms: amorphous, Polymorph A, and Polymorph B. This study investigates the molecular basis of polymorph selection, focusing on conformational bias and solvent-mediated phase transformations (SMPTs). Methods: The conformational energy landscapes of two TPZ tautomers were constructed using relaxed torsion scans with the OPLS4 force field and validated by nuclear Overhauser effect (NOE)-based nuclear magnetic resonance (NMR). Hydrogen-bonded dimers were analyzed using DFT-D. Powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), solubility, and slurry tests were conducted using methanol, acetone, and water. Kinetic profiles were modeled with the Kolmogorov–Johnson–Mehl–Avrami (KJMA) equation. Results: Polymorph A was thermodynamically stable across all analyses. Both amorphous TPZ and Polymorph B converted to A in a solvent-dependent manner. Methanol induced direct A formation, while acetone showed a B → A transition. Crystallization was guided by solution conformers and hydrogen bonding. Conclusions: TPZ polymorph selection is governed by solution-phase conformational preferences, tautomerism, and solvent-mediated hydrogen bonding. DFT-D and NMR analyses showed that protic solvents favor the direct crystallization of stable Polymorph A, while aprotic solvents promote the transient formation of metastable Polymorph B. Elevated temperatures and humidity accelerate polymorphic transitions. This crystal structure prediction (CSP)-independent strategy offers a practical framework for rational polymorph control and the mitigation of disappearing polymorph risks in tautomeric drugs. Full article