Reactions

Ozonation is one of the most widely used methods for wastewater treatment. However, it suffers from several drawbacks, including a low reaction rate, long reaction time, and the formation of intermediate byproducts due to incomplete oxidation. Therefore, in this paper, the ozonation process was improved via the MgO nanocatalyst and honeycomb activated carbon (HAC) as a packing material in the bubble column reactor by using the following methods: (O₃/MgO, O₃/HAC, and O₃/MgO/HAC). The results showed that using ozone alone yielded a low chemical oxygen demand (COD) removal efficiency of 63.33% after 90 min, and the phenol concentration was 15 mg/L. However, when the catalyst was added, the efficiency increased to 73.33%, which is attributed to the enhanced generation of more hydroxyl radicals (OH•). The HAC packing material had a positive effect, as the removal efficiency rose to 76.66% due to its effective role in improving the mass transfer inside the reactor. The integrated (O₃/MgO/HAC) method proved to be the most effective at achieving a COD removal efficiency of about 83%; furthermore, the efficiency reached 91% when the initial phenol concentration decreased to 10 mg/L. Two doses of catalysts were used, 0.05 and 0.1 g/L, and it was found that the higher dose (0.1 g/L) had the highest efficiency. The effect of the initial phenol concentration and ozone gas flow rate were studied. The study concludes that the use of the MgO nanocatalyst and the honeycomb-structured activated carbon packing material plays an effective role in improving the ozonation process by increasing the reaction rate, reducing treatment time, and decreasing the demand for additional ozone gas supplies, thus achieving significant economic benefits. Full article

This study investigates the thermochemical reaction behaviour of scheelite–millscale aluminothermy for direct tungsten alloying in steel production. Experimental mixtures of aluminium, millscale, and scheelite concentrate were simulated using gas–slag–metal (g-s-m) equilibrium calculations in FactSage 8.3 at 2200 °C, and compared with previously reported experimental results. The simulations reproduced metal yields accurately with 0.901 to 0.940 correlation coefficients and predicted tungsten levels consistent with measured steel compositions. However, significant discrepancies were observed in predicted silicon levels, with simulations overestimating steel %Si by up to 3.5%, despite negligible gas-phase losses. Oxygen partial pressure calculations indicate that the Fe/FeO reaction equilibrium controls process reduction conditions. Backcalculation of activity coefficients revealed that FactSage minimisation routines understated silicon activity coefficient values. SiO₂ mass transfer may play a role in low %Si in steel, but this is not clear due to differences in expected mass transfer regimes in aluminothermy under ASR and SHS conditions. Overall, the simulations demonstrate adequate predictive capability for alloying trends and metal yields while highlighting limitations in predicting silicon partitioning. These findings confirm the utility of thermochemical simulation for designing aluminothermic feed mixtures, reducing the number of experiments needed to optimise the aluminothermic feed mixture ratios. Full article

Ordered mesoporous carbons have emerged as versatile supports for Fischer–Tropsch catalysts due to their high surface area, tunable pore architectures, and chemical stability. However, the influence of active-metal identity on product selectivity within a common carbon framework remains insufficiently understood, particularly when Fe and Co are compared under rigorously identical conditions. To address this aspect, we prepared Fe- and Co-based catalysts with comparable nominal metal loadings supported on CMK-5 carbon material and evaluated their structural, surface, and catalytic properties. Comprehensive characterization revealed distinct metal-dependent behaviors, and catalytic testing between 423 and 598 K at 2 MPa showed that the catalyst CMK-5(Co10) exhibited substantially higher activity, whereas CMK-5(Fe10) provided a more stable product distribution and exclusively paraffinic C₂–C₃ products across the studied temperature range. In contrast, CMK-5(Co10) displayed a pronounced temperature-dependent selectivity, with increasing methane formation and the emergence of olefinic C₂–C₃ species at intermediate and high temperatures. Chain-growth probabilities were consistent with these trends. Complementary Density Functional Theory and Kinetic Monte Carlo analyses indicated stronger binding of carbonaceous intermediates on Fe clusters and more accessible C–C coupling pathways on Co clusters. Together, these results clarify how active-metal identity governs selectivity within a shared CMK-5 architecture and provide guidelines for designing carbon-supported Fischer–Tropsch catalysts with controlled product distributions. Full article

In the present article, tetra(nonyl)calix[4]resorcinarene, tetra(p-methoxyphenyl)calix[4]resorcinarene, and tetra(p-bromophenyl)calix[4]resorcinarene were synthesized by the cyclocondensation method in acid medium. In the case of tetra(nonyl)calix[4]resorcinarene, only the crown conformer was obtained, while in the case of tetra(p-methoxyphenyl)calix[4]resorcinarene and tetra(p-bromophenyl)calix[4]resorcinarene, a conformational mixture (crown and chair) was formed, separated, and purified via the recrystallization technique. Subsequently, the per-O-acetylation reaction of the pure conformers was carried out. According to the RP-HPLC and ¹H-NMR results, the per-acetylation product of the crown conformer of tetra(nonyl)calix[4]resorcinarene retained its conformation, likewise the per-O-acetylation products of the chair conformer of tetra(p-methoxyphenyl)calix[4]resorcinarene and tetra(p-bromophenyl)calix[4]resorcinarene. On the other hand, the per-O-acetylation product of crown conformers of tetra(p-methoxyphenyl)calix[4]resorcinarene and tetra(p-bromophenyl)calix[4]resorcinarene gave rise to the formation of the boat conformer. Full article

This study investigates the mechanochemical synthesis of silver molybdate (Ag₂MoO₄). Three silver precursors (AgCl, AgNO₃, Ag₂SO₄) in combination with sodium molybdate dihydrate as the molybdenum precursor were used. Three corresponding sodium salts, which are also formed as byproducts, were employed as process control agents (PCAs) to investigate the possibility of obtaining fine-grained silver molybdate. Milling was performed in a planetary mill at 600 and 100 rpm, and for 2 h, 15 min, and 5 min. X-ray diffraction analysis (XRD) revealed that AgCl is completely unreactive in this type of reaction, whereas AgNO₃ and Ag₂SO₄ form crystalline Ag₂MoO₄. Additional sample characterization included Fourier transform infrared spectroscopy (FTIR), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and simultaneous differential thermal and thermogravimetric analysis (DTA-TGA). The results indicate that the silver molybdate formation reaction is favorable and rapid. Even under the mildest conditions, including the presence of PCA, micron-sized silver molybdate particles were obtained. A greater rotation rate and longer milling time resulted in a decrease in particle size, but also an increase in sodium content. However, unlike the few existing reports on the mechanochemical synthesis of Ag₂MoO₄, which, despite harsh milling conditions, did not yield a phase-pure product, our approach produced well-crystallized and pure silver molybdate even under the mildest synthesis conditions. Full article

In this study, a novel magnetic metal–organic framework (MOF) composite, Pd@UiO-66@Fe₃O₄, was successfully synthesized as a high-performance heterogeneous catalyst for the Suzuki–Miyaura cross-coupling reaction. The material was prepared by loading nano-sized carboxylated Fe₃O₄ onto UiO-66 via an in situ solvothermal method, followed by the encapsulation of Pd nanoparticles using an ultrasound-assisted dual-solvent method (DSA). Characterization results, including PXRD and TEM, confirmed that the ternary composite retains the structural integrity of UiO-66 while incorporating magnetic functionality and well-dispersed Pd active sites. The catalyst exhibited high catalytic performance for the coupling of aryl iodides and aryl boronic acids. Furthermore, the catalyst demonstrated good compatibility with the substrates examined and excellent stability. Due to the integration of carboxylated Fe₃O₄, the composite could be easily separated from the reaction mixture using an external magnet and reused for at least five cycles without a significant loss in catalytic activity. The high activity and durability are attributed to the integrated roles of the Pd nanoparticles, the porous MOF support, and the magnetic Fe₃O₄ component, which respectively provide catalytic active sites, structural stabilization/dispersion, and magnetic recoverability. Full article

An optimum In_0.2Cd_0.8S composition was synthesized with graphene to enhance photocatalytic performance. Graphene incorporation altered the morphology from compact grains to a loosely aggregated structure without affecting the crystal phase, as confirmed by XRD. XPS analysis indicated surface-level interaction between graphene and the In–Cd–S matrix, rather than lattice integration. Mott–Schottky and Kubelka–Munk analyses revealed n-type semiconducting behavior and a slight band gap increase from 2.46 to 2.51 eV upon graphene blending. UV–Vis and IPCE measurements showed enhanced light absorption, with IPCE values of 9.33% and 5.01% at 380 nm and 480 nm, respectively. The 3.85 wt% graphene-modified photocatalyst achieved a hydrogen evolution rate of 4.97 μmolh⁻¹cm⁻², more than triple that of pristine In_0.2Cd_0.8S. These enhancements are attributed to improved charge transport and interfacial activity provided by the graphene. Full article

In this review, some special characteristics of the reactions in semiconductor photocatalysis are presented. At first, since a pair of the redox reactions take place at the same particle, a particle-based kinetic method was presented and applied for the Langmuir–Hinshelwood kinetics to describe the photocatalytic oxidation as a function of both the reactant concentration and the light intensity. Since the surface electron transfer (ET) reactions are the subject of electrochemistry, the difference in the characteristics from particulate semiconductor photocatalysis was pointed out by showing each electric potential near the solid surface. Different from ET in electrochemistry, the ET frequency is limited by the photon absorption in photocatalysis. In the estimation of the reaction rate, the validity of Marcus theory in photocatalysis was argued. Almost all photocatalytic reactions are irreversible, because, before the charge recombination, the oxidation and/or reduction must take place at the same particle. Then, the kinetics for irreversible reaction was discussed. As an exception, the reversible reduction reaction of methylviologen with a hole scavenger was presented. By changing pH, the energy levels of thermalized electrons in TiO₂ particles were estimated, and the difference of the flat band potentials between anatase and rutile was clearly explained. Thus, various uniqueness of photocatalytic reactions in aqueous suspension of semiconductor particles were demonstrated. Full article

Pure LaFeO₃@C and LaCoO₃@C and substituted LaFe_1-xCo_xO₃ and LaCo_1-xFe_xO₃ perovskites (x = 0.10; 0.30) were used as catalysts for the liquid-phase oxidation of furfural at 150 °C and 30 bar of O₂ pressure. The perovskites were characterized by XRD, H₂-TPR, N₂ physisorption, TPR-MeOH, and XPS. The carbon in situ incorporation (@C) increases the surface area, favoring oxygen mobility leading to LaFeO₃@C stabilizing the redox pair Fe³⁺/Fe²⁺. In contrast, no evidence of the formation of a LaCoO₃@C perovskite structure through @C incorporation was observed. The gradual substitution of Fe with Co (10 and 30%) in LaFeO₃@C decreases the crystallinity, redox and basic properties, and surface area. For LaCoO₃@C, after the substitution of Co with 10 and 30% of Fe, only metal (La, Fe, Co) oxides as segregated phases were observed. The highest catalytic activity and selectivity to maleic acid of LaFeO₃@C is attributed to the higher surface area, crystalline structure, and surface-reducible Fe³⁺ species, favoring oxygen mobility and promoting their more oxidizing capacity. The lower catalytic activity of LaCoO₃@C, the Co- and Fe-substituted LaFeO₃@C and LaCoO₃@C catalysts, is attributed to the smaller surface area, and the similar selectivity towards maleic acid, 5-hydroxy-2(5H) and furanone indicates that the active site type is not modified in comparison to LaFeO₃@C. Full article

N-Alkyl urazoles are important heterocyclic compounds that serve as important precursors to potent N-alkyl 1,2,4-triazoline-3,5-dione electrophiles. Traditional methods for urazole synthesis rely upon the use of toxic isocyanates. We have modified and optimized an overlooked and poorly described method from the literature for the synthesis of urazoles that now avoids the use of isocyanates, limits the use of solvents, and provides urazoles without the need for purification steps. A variety of urazoles are afforded in good to high yields. Full article

The 1,3-dipolar cycloaddition of nitrones with hydrazones affords 5-iminoisoxazolidines as the major products, in contrast to the reaction with enals, which exclusively afford 4-acylisoxazolidines. This reversal of regioselectivity can be explained in terms of frontier orbital theory. The 5-iminoisoxazolidines are easily converted to 5-acylisoxazolidines. Full article

A series of bifunctional hierarchical HZSM-5 catalysts modified with Zn, Ga, Ni, Cr, or Ag were synthesized via impregnation, and their performance in the catalytic fast pyrolysis of walnut shells was systematically evaluated. The influence of the metal species and concentration of NaOH used for desilication (0.20–0.40 mol·L⁻¹) on the yield of light aromatics was assessed. Ga/HZSM-5 and Zn/HZSM-5 exhibited the most pronounced enhancement at 0.35 mol·L⁻¹, significantly outperforming the unmodified HZSM-5. Building on this finding, Zn-Ga bimetallic hierarchical catalysts were developed, and the effect of the Zn:Ga loading ratio (1%:2%, 1.5%:1.5%, 2%:1%) was investigated. The 1%Zn/2%Ga catalyst delivered the highest performance, achieving a total aromatic yield of 3.876 × 10⁴ a.u.·mg⁻¹, with 82% BTX (benzene, toluene, and xylenes) selectivity. The term “a.u.” stands for “arbitrary units,” typically derived from peak area counts obtained through GC-MS analysis. These values represent the relative signal intensity detected by the instrument, rather than absolute quantities of the substance. To more accurately characterize the aromatic hydrocarbon yield, these data are normalized to the yield of aromatic hydrocarbons per unit mass. These findings demonstrate that the combination of Zn-Ga modification and tailored mesoporosity can markedly enhance the production of high-value benzene, toluene, and xylene (BTX) aromatics from lignocellulosic biomass. Full article

Interest in further developments of the classical Fischer–Tropsch technology has increased in recent years. The development of processes capable of producing synthetic fuels has become a highly attractive research area due to the continuous global growth in energy demand. An extensive review covering the full development chain (from laboratory-scale experiments to pilot-scale studies and plant-level implementations) is therefore of significant relevance. Consequently, this review aims to be a reference by integrating findings across different development levels of Fischer–Tropsch synthesis technologies, thereby enabling a holistic perspective of the pathway toward industrial-scale deployment. The present work thus critically reviews recent advances in catalyst development, including the role of active phases, particle size effects, supports, and promoters, as well as the growing contribution of in situ and operando characterization techniques. In parallel, progress in kinetic and mechanistic modeling is discussed, highlighting both classical approaches and emerging data-driven and optimization-based methods. Different reactor technologies, from classical to novel technologies, are also analyzed with respect to hydrodynamics, heat and mass transfer limitations, and reactor intensification strategies. At the process level, the review assesses integrated and intensified Fischer–Tropsch-based routes, with particular emphasis on CO₂ utilization pathways, process integration, polygeneration schemes, and optimization frameworks. The potential of artificial intelligence and machine learning tools to accelerate catalyst discovery, reactor optimization, and process design is also addressed. Overall, this review identifies key technological advances, remaining challenges, and research gaps that must be addressed to enable economically viable and environmentally sustainable, and scalable Fischer–Tropsch processes to meet future energy demands. Full article

This study presents a transient mathematical model and its numerical solution for the moving-boundary problem related to substrate diffusion and reaction in enzymatic catalytic particles. The main focus is on bioreactor startup, where the initial substrate concentration inside the particles is zero, forming a dead core that shrinks over time and makes the catalytic effectiveness factor time-dependent. The substrate mass balance leads to a partial differential equation with a moving boundary, solved using the method of lines coupled with Newton’s method (MLN), implemented in Wolfram Mathematica (WM). The proposed approach was validated for zero- and first-order kinetics at steady state, whose analytical solutions are available. Compared to the method of orthogonal collocation on finite elements, the MLN offers advantages such as not requiring an initial concentration profile and simple implementation in WM. The results demonstrate that the proposed method provides accurate and physically consistent solutions, contributing to a better understanding of dead-core dynamics and supporting the design of heterogeneous bioreactors with immobilized enzymes. Full article

Red Amaranth (RA) Azo dye is a persistent pollutant in wastewater and stands as a toxicological risk, which has led to the development of effective methods for its removal and photocatalytic degradation. Therefore, CeO₂ nanoparticles were synthesized by a controlled precipitation method, and Ultraviolet-Visible (UV–Vis) analysis and Tauc plots yielded a band gap of ~3.24 eV. The CeO₂ nanoparticles showed the fluorite cubic phase, and nearly spherical particles with an average size of ~10 nm. Nitrogen physisorption revealed a type IV isotherm with a Brunauer–Emmett–Teller (BET) surface area of 85.27 m²·g⁻¹ and a total pore volume of 0.27 cm³·g⁻¹, indicating a mesoporous structure and high surface accessibility. The chemical behavior showed Ce and O, consistent with phase purity. Photocatalytic performance was evaluated in 20 ppm aqueous solution of RA under 365 nm UV irradiation (LED 100 W), with a temperature of ~20 °C and a 15 min dark adsorption step. Concentration decay was followed at λ_max = 520 nm by Lambert–Beer. The degradation efficiency η and pseudo-first-order kinetic were obtained from ln(C₀/C_t) vs. time. In addition, chemical oxygen demand (COD) tests were performed on RA solution before and after photodegradation, showing a COD reduction of ~85% (from 19.8 to 3 mg O₂·L⁻¹), which corroborates mineralization beyond chromophore bleaching. Under [C₀ = 20 mg·L⁻¹] and [m_cat = 1.0 g·L⁻¹], CeO₂ achieved [RA = 90% at 180 min, k = 0.0125 min⁻¹]. These results demonstrate that CeO₂ is an effective photocatalyst for RA degradation under UV-A irradiation, integrating adsorption, kinetic behavior, and mineralization performance into a coherent structure–property relationship. Full article

This work presents the synthesis, characterization, and application of zirconium oxide (ZrO₂)-based catalysts, modified with macro (silica nanospheres, NSP-SiO₂) and mesopore templates (Pluronic 123), impregnated with tungstophosphoric acid (TPA), in the catalytic pyrolysis of tomato agro-industrial residues. The NSP-SiO₂ (SXX) and P123 (PYY) amount mainly influences the ZrO₂SXXPYY-specific surface area (S_BET) and average pore diameter (D_p). ³¹P MAS NMR and FT-IR characterization results show that TPA (H₃PW₁₂O₄₀) was partially transformed into [P₂W₂₁O₇₁]⁶⁻ and [PW₁₁O₃₉]⁷⁻ during the synthesis steps. The acidic properties of ZrO₂SXXPYY samples containing 25 and 50 wt% of TPA (ZrO₂SXXPYYT25 and ZrO₂SXXPYYT50, respectively) are dependent on both the TPA content and the support nature. Bio-oil composition and product selectivity were strongly influenced by the textural and acid-based properties of the catalysts. Notably, non-catalytic pyrolysis favored pathways leading to C2 compounds, with a high content of acetic acid and hydroxyacetone. In contrast, the use of catalysts promoted the formation of higher molecular weight oxygenated compounds (C5–C6), specifically furans, aldehydes, and ketones. Full article

Linear alkylbenzene (LAB) is the main raw material used to make biodegradable detergents, and its production process is based on aromatic alkylation. HY zeolites that have undergone controlled dealumination and desilication have led industrial standards amongst solid acid catalysts because of their controllable acidity and hierarchical pore structure. Coke formation in such systems can assume a dual role, which is dependent on its condition. Though the over-deposition is known to cause deactivation by blocking the micropores, Bronsted acid-site masking, and diffusion collapse, the low-level deposition could also be done to increase the monoalkylate selectivity by the pore mouth catalysis, steric modulation, and selective suppression of secondary alkylation pathways. The critical review is done on the structural-kinetic interaction that determines the coke evolution in HY-based catalysts. In order to moderate the acid-site density and enhance hydrothermal stability, dealumination (Si/Al optimization of about 2.5 to 30–100) occurs, but to reduce deep-pore coke formation, desilication (interconnected mesopores) is created. The bimodal porosity and regulated acidity are found to be synergistic, as hierarchical HY zeolites produced through successive cycles of steam and alkaline treatments not only show LAB selectivity in excess of 90% but also exhibit much longer catalyst lifetimes. Quantitative research on the beneficial coke regime revealed that it was composed of about 36 wt% hydrogen-rich species, which were localized at the pore mouths, hence enhancing monoalkylation selectivity by 15–40%. Beyond a critical transition window (e.g., 8–12 wt.%), coke formation to condensed polyaromatic and graphitic products leads to fast deactivated coke formation, which is due to percolation limits and transport-controlled kinetics. More advanced techniques of characterization of the coke, e.g., temperature-programmed oxidation (TPO), ²⁷Al MAAS NMR, and UV-Raman spectroscopy, indicate how the coke is changed to highly structured graphitic deposits of high oxidation activation energy. Activity recovery of 85–98% is obtained in regeneration processes, including controlled oxidative calcination, microwave-based and plasma-based processes, and thermal management protocols, and it would be determined by the chemistry of the coke, its spatial distribution, and the regeneration protocols. This paper has developed a mechanistic coke control system by cross-tuning the acidity and development of an effective pore network, which led to a sustainable aromatic alkylation reaction with minimal activity loss, high selectivity, and long life. Full article

Rhizopus oryzae lipase (ROL) is a key enzyme involved in olive oil spoilage and acts as a virulence factor in fungal infections. Natural lipophilic lipase inhibitors are crucial for mitigating economic losses resulting from lipid degradation in stored or decaying olive fruits. This study evaluated a series of enzymatically synthesized piperate esters with varying alkyl chain lengths (butyryl, C4; octyl, C8; dodecyl, C12) for their inhibitory effects on ROL activity. Octyl piperate (C8) demonstrated the highest potency, with IC₅₀ values of 0.05 mg/mL using methods B and C or 0.25 mg/mL using method A. Molecular docking indicated that C8 achieved the most favorable predicted binding energy (Gscore: –11.134 kcal/mol), primarily through hydrophobic interactions (Val329, Ala212, Phe209) and hydrogen bonds with oxyanion hole residues (Ser268, Thr206, Gln241). Molecular dynamics simulations confirmed that C8 maintained stable binding and stabilized the catalytic residues. In comparison, C4 exhibited weaker interactions, and the longer C12 chain induced conformational instability and steric hindrance. These results establish a parabolic structure–activity relationship, identifying the octyl chain (C8) as optimal for ROL inhibition among the tested derivatives. The rational design of lipophilic, biodegradable lipase inhibitors thus positions octyl piperate as a promising candidate for extending olive storage and shelf life, and as a scaffold for developing natural antifungal agents targeting virulent R. oryzae strains. Full article