Search Results (841)

In this study, the thermodynamic conditions governing TiC formation were systematically investigated based on Gibbs free energy and interaction parameter theory. The effects of temperature and furnace atmosphere on interaction parameters were explicitly incorporated, enabling an improved thermodynamic description of TiC formation under realistic blast furnace conditions. Furthermore, compared with conventional two-dimensional equilibrium analyses, a three-dimensional Ti-C-temperature thermodynamic precipitation surface was established to quantitatively evaluate the effects of temperature, titanium content, and carbon content on TiC precipitation behavior. The results indicate that titanium is the dominant controlling factor for TiC formation, while carbon plays a secondary synergistic role. Compared with dissolved carbon, solid carbon provides more favorable thermodynamic conditions, suggesting that TiC preferentially forms via interactions with high-activity carbon sources such as coke or refractory materials. Based on the modified thermodynamic framework and boundary conditions, a quantitative precipitation criterion was established as 100 × w[Ti]_% + w[C]_% ≥ 10, which ensures TiC precipitation prior to molten iron solidification under representative blast furnace hearth conditions. The proposed criterion provides a practical guideline for titanium addition and carbon regulation in blast furnace ironmaking and improves the thermodynamic prediction capability for titanium-bearing protective phase formation in complex high-temperature metallurgical environments. Full article

Among the various CO₂ capture technologies, chemical absorption is currently one of the most widely applied methods in industrial practice. In this study, density functional theory was employed to investigate the reaction mechanisms of CO₂ absorption by typical alkanolamine solvents. Reaction pathways between CO₂ and four representative alkanolamines—monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), and methyldiethanolamine (MDEA)—were constructed and analyzed. By evaluating the activation energy barriers of different amines, the thermodynamic characteristics and reaction feasibility of the CO₂ absorption process were systematically elucidated. The results show that the primary amine MEA exhibits the lowest activation energy barrier (32.02 kJ/mol), indicating the most favorable reaction kinetics, while the secondary amine DEA shows a slightly higher barrier of 47.35 kJ/mol. As tertiary amines, TEA and MDEA exhibit significantly higher activation energy barriers, indicating slower reaction kinetics; however, they generally possess higher CO₂ loading capacities and less stable reaction products, which facilitate solvent regeneration. The activation energy barriers of MDEA and TEA were calculated to be 54.53 kJ/mol and 94.17 kJ/mol, respectively, indicating that MDEA reacts more readily with CO₂ than TEA. Full article

Aromatic compounds are abundant in urban and industrial environments and potentially serve as one of the primary precursors for new particle formation (NPF). Pi-pi stacking is a distinctive weak interaction observed between aromatic compounds. Aromatic oxygenated organic molecules (AOOM) are key products of atmospheric oxidation of aromatic compounds; however, the role of pi-pi stacking in their involvement in atmospheric new particle formation (NPF) remains unclear. This study used quantum chemical calculations to reveal the nucleation mechanism of AOOM through pi-pi stacking and hydrogen bonding. The results indicate that the contribution of pi-pi stacking to nucleation in aromatic compounds is primarily determined by the stacking area. For aromatic hydrocarbons with 1–2 phenyl groups, the Gibbs free energy (ΔG) of dimolecular clusters formed solely by pi-pi stacking is positive. In contrast, for polycyclic aromatic hydrocarbons with three or more phenyl groups, the ΔG of these clusters decreases significantly and becomes negative. Single-phenyl AOOM primarily participates in the NPF process through hydrogen bonding with sulfuric acid molecules. In this work, an explanation is provided for observations and laboratory findings of the appearance of aromatic-ring-retaining species in nanoparticles. The discovery of pi-pi stacking also completes the variety of atmospheric nucleation weak interactions. The oxidation and nucleation mechanisms of aromatic compounds should be reassessed, considering the effects of pi-pi stacking, especially polycyclic aromatic hydrocarbons. These findings have important implications for sustainable urban air-quality management. By clarifying the role of pi-pi stacking, particularly in polycyclic aromatic hydrocarbons, this study may improve predictions of new particle formation, refine secondary organic aerosol modeling, and inform targeted emission-control policies to protect public health and mitigate climate impacts. Full article

To address the resource waste caused by the ineffective recycling of large quantities of red mud, this study proposes an innovative technical route consisting of red mud sintering followed by smelting in a small blast furnace or solid-waste smelting furnace for pyrometallurgical iron extraction. Under optimized process conditions—binary basicity of 4.97, a raw material composition of 78.27% wet-based red mud, 15.67% quicklime, and 6.05% fuel, with a solid fuel consumption of 121 kg/t—the produced sinter meets the feeding requirements of blast furnace smelting. The results indicate that the liquid phase generated during red mud sintering mainly consists of composite oxides in the CaO–Al₂O₃–SiO₂ system; calcium aluminosilicate (Ca₂Al₂SiO₇) was detected and inferred to be a potential bonding phase in the sinter matrix. Thermodynamic analysis shows that the Gibbs free energy of Ca₂Al₂SiO₇ is lower than that of calcium ferrite, indicating that its formation is thermodynamically more favorable. The formation amount of this phase is closely related to the Ca/Al ratio, while temperature has a limited influence. In addition, Na₂O can react with CaO·2 Al₂O₃ to form a low-melting-point phase, which significantly reduces the sintering temperature and enhances the fluidity of the liquid phase. These findings provide a new theoretical basis for the sintering of high-alumina ores and offer technical support for the efficient utilization of red mud as well as energy conservation and emission reduction. Full article

In this study, manganese ferrite was grown on the surface of a low-cost powder substrate of a guava leaf using the co-precipitation method. The resulting material was characterized using various spectroscopic and microscopic techniques. The composite was formed through the electrostatic and non-electrostatic interactions between the manganese ferrite nanoparticles, and the functional groups present on the guava leaf substrate; consequently, a high content of functional groups was observed in the synthesized composite through the Fourier transform infrared spectroscopy. The average size of the nanoparticles grown on the guava leaf substrate was determined to be between 3 and 5 nanometers. The synthesized composite material was utilized for adsorption applications, employing Methylene blue dye as a model adsorbate. Methylene blue was removed from the aqueous solutions under various conditions—including variations in the pH, contact time, temperature, and concentration. Under optimal conditions, it was observed that an adsorbent dosage of 2 g L⁻¹ was capable of removing approximately 99% of the dye from a 10 mg L⁻¹ dye solution at pH 7. The dye removal efficiency (%) decreased with the increasing temperature, indicating an exothermic process; this was further confirmed by the thermodynamic parameter analysis (specifically, the change in enthalpy, or ΔH), which yielded a negative value. Gibbs Free Energy (ΔG) also yielded a negative value, signifying the feasibility and spontaneity of the adsorption process. In this study, the adsorption process followed the Freundlich isotherm model, with the value of ‘n’ falling between 1 and 10, which is indicative of heterogeneous adsorption. The adsorption kinetics were determined to follow a pseudo-second-order model, and the overall rate-limiting step of the process was identified as intraparticle diffusion. To assess the sustainability and stability of the adsorbent, regeneration and reusability experiments were conducted. The results revealed that the modified guava leaf performed effectively for up to five cycles, achieving an adsorption efficiency of approximately 24% after the final cycle. Thus, the developed adsorbent proved to be an effective material for the removal of Methylene blue dye. Full article

We designed a supervised machine learning framework to predict standard Gibbs free energies, ΔG°, of formal hydrogen atom transfer (f-HAT) for phenolic antioxidants across different radicals and media, enabling rapid and chemically interpretable screening. We curated a DFT dataset of 71 molecules (phenolic compounds and anthocyanidins), with 207 reaction sites, 10 radical reactive oxygen/sulfur species, and three environments (leading to a total of 6210 ΔG° values). The models amass 106 numerical RDKit descriptors, augmented with one-hot encodings of medium, site, radical, and structural class, and were evaluated through a leave-one-molecule-out protocol. Among the tested regression algorithms, the random forest regressor provides the best balance of accuracy and robustness with both R² test (≈0.94) and MAE (2.74 kcal mol⁻¹; RMSE (≈5.0 kcal mol⁻¹)), close to DFT chemical accuracy. The feature-importance analysis revealed that “electronic” and “experimental” (site/group) descriptors primarily drive predictions, with the radical’s maximum absolute partial charge being the most important descriptor in the prediction of a radical’s ΔG°. These results suggest that descriptor-driven RF (Random Forest) models can generalize across chemical space to provide interpretable ΔG° predictions, providing a path for chemists towards a scalable route to prioritize antioxidant candidates for broader molecular families. Full article

This work focused on synthesizing MgSiO₃ (0%Mo@MgSi), 2.5%MoO3@MgSiO₃ (2.5%Mo@MgSi), 5%MoO₃@MgSiO₃ (5%Mo@MgSi), and 10%MoO₃@MgSiO₃ (10%Mo@MgSi) by a single-step process utilizing butylated hydroxytoluene (BYHT) as a novel capping agent. The X-ray diffraction analysis of the synthesized nanohybrids indicated amorphous nanohybrids, while the energy-dispersive X-ray spectroscopy results illustrated variations in the MoO₃ doping dosages. The 0%Mo@MgSi, 2.5%Mo@MgSi, 5%Mo@MgSi, and 10%Mo@MgSi nanohybrids exhibited average sizes of 17.6, 12.2, 11.7, and 9.9 nm, respectively, and surface areas of 43.53, 40.95, 42.17, and 44.98 m²·g⁻¹, respectively. The examination of 0%Mo@MgSi, 2.5%Mo@MgSi, 5%Mo@MgSi, and 10%Mo@MgSi nanohybrids toward the oxytetracycline (OTC) sorption resulted in q_t values of 72.89, 116.89, 98.39, and 78.46 mg·g⁻¹, respectively. The OTC sorption onto the 0%Mo@MgSi, 2.5%Mo@MgSi, 5%Mo@MgSi, and 10%Mo@MgSi aligned with the nonlinear pseudo-second order model, and both the intraparticle and liquid-film diffusion models co-influenced the OTC sorption onto the four nanohybrids. Increasing the temperature decreased OTC sorption on 2.5%Mo@MgSi, indicating exothermic sorption. The Langmuir isotherm model was more suitable than the Freundlich model for describing OTC adsorption on 2.5%Mo@MgSi. The Dubinin–Radushkevich energy (E_D ≤ 8.0 kJ·mol⁻¹) and the Gibbs free energy (ΔG° ≤ 20 kJ·mol⁻¹) supported each other’s outcomes about the OTC removal onto 2.5%Mo@MgSi being via physisorption. The ΔG° values increased proportionally with temperature, indicating that OTC sorption becomes more spontaneous as temperature decreases. Moreover, the 2.5%Mo@MgSi exhibited excellent stability in OTC elimination up to the third cycle. Full article

Sulfate roasting is a critical pyrometallurgical pre-treatment for extracting Cu and Co from low-grade Cu–Co–Fe sulfide ores, yet conventional phase diagrams provide limited quantitative guidance for process control. To address this gap, a multicomponent/multiphase thermodynamic equilibrium model based on Gibbs free energy minimization was developed to systematically investigate the oxidative roasting behavior of single sulfides (Cu₂S, CoS₂, FeS₂) and their ternary mixture, with respect to air supply, temperature, and total pressure. The model reveals that each sulfide follows distinct, temperature-dependent phase transformation pathways: Cu₂S forms the acid-leachable product CuO·CuSO₄ at temperatures ≤ 588 °C with a stoichiometric air supply of 11.9 mol, transitioning to oxides at ≥800 °C; CoS₂ converts completely to CoSO₄ below 727 °C and to CoO at higher temperatures; FeS₂ yields sulfate phases at low temperatures and iron oxides above 654 °C. In the ternary Cu₂S–CoS₂–FeS₂ system, competitive oxidation reactions produce refractory mixed oxides (CuO·Fe₂O₃, CoO·Fe₂O₃) whose formation is governed by temperature, air supply, and sulfide molar ratios. The results demonstrate that low-temperature roasting (≤641 °C) with precisely controlled air supply maximizes the formation of water-soluble sulfates, providing a quantitative thermodynamic basis for process optimization and enhanced recovery of Cu and Co from complex sulfide ores. Full article

This study presents a thermodynamic analysis of the dissociation and association behavior of the Fe–Si system using the Bjerrum–Guggenheim osmotic coefficient. An equilibrium thermodynamic approach was applied to evaluate the Gibbs free energy, equilibrium constant, and degree of association of the congruently melting compound FeSi over a wide temperature range. The Fe–Si system was analyzed across three characteristic crystallization regions: Fe-rich, FeSi, and Si-rich. It was established that the Fe-rich region exhibits behavior approaching ideality with a nearly linear dependence of the osmotic coefficient, whereas the Si-rich region is characterized by strong deviations from ideality due to intensive association processes. The FeSi crystallization region represents a transitional regime in which association and dissociation processes occur simultaneously. The formation and partial dissociation of [Fe_xSi_y] clusters significantly affect the thermodynamic behavior of the melt. It was shown that accounting for FeSi dissociation leads to a linearization of the osmotic coefficient dependence and improves the accuracy of thermodynamic description. The proposed analytical approximations demonstrate high correlation coefficients (R² ≈ 0.99), confirming the reliability of the developed approach. The results provide a consistent thermodynamic framework for describing phase transformations and structural evolution in Fe–Si melts and can be applied to the optimization of metallurgical processes involving silicon-containing alloys. Full article

This study investigates the thermodynamic and kinetic features of chromium reduction from chromium ore using complex Fe–Si–Cr and Al–Si–Cr alloys as reducing agents for the refined ferrochrome production. The thermodynamic probability of Cr₂O₃ reduction by silicon and aluminum was evaluated using thermodynamic equilibrium calculations based on reference thermodynamic data, including determination of the standard Gibbs free energy change over the studied temperature range. The results showed that both reduction routes are thermodynamically feasible, while aluminum exhibits a higher affinity for oxygen and a greater reducing capacity. The thermal behavior of chromium ore and its mixtures with Fe–Si–Cr and Al–Si–Cr alloys was studied by differential thermal and thermogravimetric analysis. The use of Al–Si–Cr, especially in briquetted form, was found to shift several thermal transformation stages to lower temperatures and to reduce the apparent activation energy of the high-temperature interaction stages compared with Fe–Si–Cr-containing mixtures. The obtained results indicate that Al–Si–Cr alloy is a promising complex reductant for intensifying chromium recovery and improving process conditions in refined ferrochrome production. Full article

This study presents a definitive framework for Cocos nucifera (coconut) shell valorization, integrating high-resolution thermogravimetry with advanced machine learning. Physicochemical analysis confirms a high-energy feedstock (45.7% carbon, 71.5% volatiles), with SEM/XEDS and FTIR revealing heterogeneous, lignocellulosic, catalytic-rich structural matrix. TG/DTG analysis identified distinct degradation windows: hemicellulose (135–395 °C), cellulose (270–430 °C), and protracted lignin decomposition (275–675 °C). Kinetic modeling indicates that pyrolysis follows a third-order (F3) continuous degradation mechanism across the studied range, supported by high correlation coefficients ($R^2$ = 0.93–0.96). The mean kinetic and thermodynamic parameters—specifically an activation energy of 165 kJ·mol⁻¹ (calculated across the 10–60 wt% conversion range during hemicellulose and cellulose pyrolysis), a positive activation enthalpy (159 kJ·mol⁻¹), and a Gibbs free energy of activation (155 kJ·mol⁻¹)—suggest that the thermochemical conversion of coconut shell is an endothermic, non-spontaneous process with moderate energy requirements. Furthermore, the integration of kNN machine learning yielded near-perfect predictive metrics ($R^2\approx 1.000$) using optimized hyperparameters ($k=85$ for TG, $k=100$ for DTG, and $k=50$ for conversion). These findings suggest that coconut shells can be efficiently valorized as a high-energy feedstock, with data enabling reliable and optimized prediction of thermal degradation to minimize experimental waste. Full article

As a strategically important metal, vanadium (V) plays a crucial role in resource security, and its efficient extraction is therefore of great significance. Traditional sodium roasting processes suffer from gaseous pollutant emissions and high costs, while calcification roasting–acid leaching has emerged as an alternative due to its environmental friendliness and economic viability. This study focuses on VTS (mainly composed of FeV₂O₄ and Fe₂SiO₄), systematically optimizing the calcification roasting–hydrochloric acid leaching process and investigating its reaction mechanism. By comparing the Gibbs free energy changes of reaction products and the acid leaching process with different additives using DFT calculations, calcium oxide was selected as the optimal calcifying agent. Experimental results show that CaO significantly promotes the transformation of FeV₂O₄ into soluble calcium vanadate and preferentially reacts with SiO₂ to inhibit vanadate encapsulation, creating a structural basis for the selective dissolution of V. Under optimal process conditions, the leaching efficiency of V can reach 94.23%. Furthermore, density functional theory (DFT) calculations substantiate that the inherently weak bonding in Ca₂V₂O₇ facilitates its effortless dissociation during the acid leaching phase. The Douglas hierarchical decision-making method is further adopted for secondary economic potential, and this proposed method has the lowest investment risk. This study provides an experimental and theoretical basis for the efficient and clean extraction of vanadium. Full article

In this study, we evaluated various density functional theory (DFT) methods to obtain thermodynamic parameters, such as enthalpy and Gibbs free energy, and compared them with experimental values obtained from conductometric analysis. As a model system, we chose the heptakis(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) complex with the recently synthesized fluorinated compound, butane-1,4-diyl bis(2,2,2-trifluoroethane-1-sulfonate) (BFS). The analysis was carried out in the temperature range of 293.15–313.15 K. A conformational search was performed to identify the most stable complexes. The final stage of optimization was conducted at the ωB97X-D4/6-31G(d,p) level of theory in the presence of water, modeled using the conductor-like polarizable continuum model (CPCM). The thermodynamic analysis indicates that almost all theoretical methods overestimate the enthalpy and Gibbs free energy. This also applies to Minnesota functionals, which are commonly recommended for thermochemistry studies. The best agreement with experimental results was obtained for the composite methods r²SCAN-3c and PBEh-3c, with the coefficient of determination (R² = 0.9972) indicating excellent correlation between r²SCAN-3c and experiment. Full article

Aflatoxin B1 (AFB1) is a potent mycotoxin threatening food and feed safety. Here, we report the identification and characterization of a Bacillus safensis-derived multicopper oxidase (BsaMCO) capable of efficient AFB1 detoxification. Recombinant BsaMCO exhibited robust in vitro activity, achieving >78% degradation of AFB1 under 24 h incubation at 37 °C. Optimization experiments revealed that enzyme concentration, pH, temperature, metal ions, and electron acceptors significantly influenced degradation efficiency, defining an operational window suitable for practical applications. LC–MS profiling suggested the presence of transformation products tentatively consistent with oxidative demethylation to aflatoxin P1 (AFP1) and with the formation of AFG2a-like products through subsequent hydration- and oxidation-related transformations. Molecular docking and 100 ns all-atom molecular dynamics (MD) simulations demonstrated stable binding of AFB1 in the T1 copper pocket. Van der Waals and electrostatic interactions, together with a persistent hydrogen bond at Gly323, facilitated single-electron transfer through the intramolecular T2/T3 copper cluster. Principal component and Gibbs free energy analyses confirmed a low-energy, stable conformational ensemble. HepG2 cell assays indicated that BsaMCO-degraded products substantially reduced cytotoxicity and apoptosis compared with native AFB1. Simulated feed experiments further validated enzymatic AFB1 degradation, with approximately 53% reduction after 24 h. Collectively, these findings establish BsaMCO as a safe and effective biocatalyst for AFB1 detoxification, providing mechanistic, structural, and cellular evidence supporting its application in food and feed safety. Full article

This study investigates the phase formation and smelting process of a complex Al-Si-Mn alloy based on thermodynamic diagram analysis (TDA). The Fe-Si-Mn-Al system was analyzed considering binary and ternary subsystems, and the standard Gibbs free energy of formation of selected ternary compounds was calculated using the additive method. Based on these results, phase equilibrium diagrams were constructed, and the system was tetrahedralized, leading to the identification of 15 thermodynamically stable tetrahedra. It was established that compositions of industrial interest are predominantly localized within tetrahedra enriched in silicide and aluminosilicide phases, particularly FeSi-Fe₂Al₂Si-Fe₃Al₁₁Si₆-Mn₅Si₃. Experimental verification was carried out in a 250 kVA ore-thermal furnace using manganese ore, high-ash coal, and quartzite. The smelting process was conducted under slag-free conditions with stable electrical operation. The obtained alloy had the following composition (wt.%): Fe ~ 12.1, Si ~ 44.7, Mn ~ 34.5, and Al ~ 5.1, with low impurity levels (C < 0.5%, S < 0.02%, p < 0.09%). Microstructural analysis using SEM-EDS confirmed the formation of silicide (FeSi, Mn₅Si₃) and aluminosilicide phases, which ensure the structural stability of the alloy. It is shown that the localization of alloy compositions within specific tetrahedra of the Fe-Si-Mn-Al system prevents self-disintegration. The results demonstrate that TDA is an effective tool for predicting phase composition and optimizing the production technology of complex ferroalloys. Full article