Search Results (929)

This research contributes to advance the sustainable production of biofuels and provides insights into the energy and exergy assessment of bio-oil, which is essential for developing environmentally friendly energy production solutions. Energy and exergy analyses were performed to evaluate the pyrolysis of beech wood biomass at 500 °C in an Auger reactor. To improve the quality of the obtained bio-oil, its catalytic deoxygenation was performed within an in-line fluidized catalytic bed reactor using a catalyst based on HZSM5 zeolite modified with 5 wt.% Iron (5%FeHZSM-5). A thermodynamic analysis of the catalytic and non-catalytic pyrolysis system was carried out, as well as a comparative study of the calculation methods for the energy and exergy evaluation for bio-oil. The required heat for pyrolysis was found to be 1.2 MJ/kg_biomass in the case of non-catalytic treatment and 3.46 MJ/kg_biomass in the presence of the zeolite-based catalyst. The exergy efficiency in the Auger reactor was 90.3%. Using the catalytic system coupled to the Auger reactor, this efficiency increased to 91.6%, leading to less energy degradation. Calculating the total energy and total exergy of the bio-oil using two different methods showed a difference of 6%. In the first method, only the energy contributions of the model compounds, corresponding to the major compounds of each chemical family of bio-oil, were considered. In contrast, in the second method, all molecules identified in the bio-oil were considered for the calculation. The second method proved to be more suitable for thermodynamic analysis. The novelties of this work concern the thermodynamic analysis of a coupled system of an Auger biomass pyrolysis reactor and a fluidized bed catalytic deoxygenation reactor on the one hand, and the use of all the molecules identified in the oily phase for the evaluation of energy and exergy on the other hand. Full article

Herein, we rationally designed a molecular catalytic filter for effective micropollutants decontamination via peroxymonosulfate (PMS) activation. Specifically, iron phthalocanine (FePc) molecules with defined Fe–N₄ coordination were immobilized onto carbon nanotubes (CNTs), forming a hybrid catalyst that integrated molecular precision with heterogeneous catalytic properties. The resulting CNT-FePc filter achieved a 98.4% removal efficiency for bisphenol A (10 ppm) in a single-pass operation system, significantly outperforming the CNT/PMS system without FePc (41.6%). Additionally, the CNT-FePc/PMS system demonstrated remarkable resistance to performance inhibition by common water matrix components. Unlike typical radical-dominated PMS activation processes, mechanistic investigations confirmed that the CNT-FePc/PMS system selectively promoted singlet oxygen (¹O₂) generation as the primary oxidative pathway. Density functional theory (DFT) calculations revealed that PMS exhibited stronger adsorption on FePc (−3.05 eV) compared to CNT (−2.86 eV), and that FePc effectively facilitated O–O bond elongation in PMS, thereby facilitating ¹O₂ generation. Additionally, seed germination assays indicated a significant reduction in the biotoxicity of the treated effluents. Overall, this work presents a catalyst design strategy that merges molecular-level coordination chemistry with practical flow-through configuration, enabling rapid, selective, and environmentally benign micropollutant removal. Full article

Nowadays, nanosized mesoporous oxides are of increasing interest to scientists. They can be used as components of heterogeneous catalysts, for photo- and electrocatalysis, as gas sensors, etc. For instance, the desired properties in catalysts include a nano size and homogeneity of the particles that form the catalyst. The particle sizes of oxides are set at the initial stage of their formation, as precursors of precipitation in the context of wet chemistry. The creation of optimal conditions is possible through the use of homogeneous precipitation, where the precipitant is formed within the solution itself as a result of a hydrolysis reaction. The resolution of this issue involved the utilization of urea in our experimental setup, obtaining the hydrolysis products of ammonia and carbon dioxide. Consequently, precipitation reactions can be utilized to obtain hydroxides, carbonates, or hydroxy carbonates of metals. The precursors were calcined, obtaining nanosized mesoporous oxides, which can have a wide range of applications. Nanosized 0.1–50 nm metal oxides were obtained, including those aluminum, iron, indium, zinc, nickel, and cobalt. Full article

Anion exchange membrane (AEM) water electrolysis is a potentially inexpensive and efficient source of hydrogen production as it uses effective low-cost catalysts. The catalytic activity and performance of nickel iron oxide (NiFeO_x) catalysts for hydrogen production in AEM water electrolyzers were investigated. The NiFeO_x catalysts were synthesized with various iron content weight percentages, and at the stoichiometric ratio for nickel ferrite (NiFe₂O₄). The catalytic activity of NiFeO_x catalyst was evaluated by linear sweep voltammetry (LSV) and chronoamperometry for the oxygen evolution reaction (OER). NiFe₂O₄ showed the highest activity for the OER in a three-electrode system, with 320 mA cm⁻² at 2 V in 1 M KOH solution. NiFe₂O₄ displayed strong stability over a 600 h period at 50 mA cm⁻² in a three-electrode setup, with a degradation rate of 15 μV/h. In single-cell electrolysis using a X-37 T membrane, at 2.2 V in 1 M KOH, the NiFe₂O₄ catalyst had the highest activity of 1100 mA cm⁻² at 45 °C, which increased with the temperature to 1503 mA cm⁻² at 55 °C. The performance of various membranes was examined, and the highest performance of the tested membranes was determined to be that of the Fumatech FAA-3-50 and FAS-50 membranes, implying that membrane performance is strongly correlated with membrane conductivity. The obtained Nyquist plots and equivalent circuit analysis were used to determine cell resistances. It was found that ohmic resistance decreases with an increase in temperature from 45 °C to 55 °C, implying the positive effect of temperature on AEM electrolysis. The FAA-3-50 and FAS-50 membranes were determined to have lower activation and ohmic resistances, indicative of higher conductivity and faster membrane charge transfer. NiFe₂O₄ in an AEM water electrolyzer displayed strong stability, with a voltage degradation rate of 0.833 mV/h over the 12 h durability test. 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 (ΔH′) 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

Steel pickling sludge serves as a valuable iron source for synthesizing Fe-based catalysts in heterogeneous advanced oxidation processes (AOPs). Here, MoS₂@CoFe₂O₄ catalyst derived from steel pickling sludge was prepared via a facile solvothermal approach and utilized to activate peroxymonosulfate (PMS) for tetracycline hydrochloride (TCH) degradation. Comprehensive characterization using scanning electron microscopy (SEM)-energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) confirmed the supported microstructure, composition, and crystalline structure of the catalyst. Key operational parameters—including catalyst dosage, PMS concentration, and initial solution pH—were systematically optimized, achieving 81% degradation efficiency within 30 min. Quenching experiments and electron paramagnetic resonance (EPR) analysis revealed SO₄^∙− as the primary oxidative species, while the catalyst maintained high stability and reusability across cycles. TCH degradation primarily occurs through hydroxylation, decarbonylation, ring-opening, and oxidation reactions. This study presents a cost-effective strategy for transforming steel pickling sludge into a high-performance Fe-based catalyst, demonstrating its potential for practical AOP applications. Full article

Fenton oxidation can contribute to meeting effluent standards for COD in actual wastewater treatment plant effluents. However, Fenton oxidation is prone to produce iron sludge waste. The application of heterogeneous Fenton-like systems based on Fenton iron mud carbon in wastewater treatment plants is essential for Fenton iron mud reduction and recycling. In this study, a Fenton iron mud carbon catalyst/Ferrate salts/H₂O₂ (FSC/Fe(VI)/H₂O₂) system was developed to remove chemical oxygen demand (COD) from secondary effluents at the pilot scale. The results showed that the FSC/Fe(VI)/H₂O₂ system exhibited excellent COD removal performance with a removal rate of 57% under slightly neutral conditions in laboratory experiments. In addition, the effluent COD was stabilized below 40 mg·L⁻¹ for 65 days at the pilot scale. Fe(IV) and ¹O₂ were confirmed to be the main active species in the degradation process through electron paramagnetic resonance (EPR) and quenching experiments. C=O, O-C=O, N sites and Fe⁰ were responsible for the generation of Fe(IV) and ¹O₂ in the FSC/Fe(VI)/H₂O₂ system. Furthermore, the cost per ton of water treated by the pilot-scale FSC/Fe(VI)/H₂O₂ system was calculated to be only 0.6209 USD/t, further confirming the application potential of the FSC/Fe(VI)/H₂O₂ system. This study promotes the engineering application of heterogeneous Fenton-like systems for water treatment. Full article

The Mo:BiVO₄/FeOOH photoelectrode was synthesized through the deposition of FeOOH onto the surface of the Mo:BiVO₄ photoelectrode. The composite photoelectrode demonstrated a photocurrent of 1.8 mA·cm⁻², which is three times greater than that observed for pure BiVO₄. Furthermore, the glycerol conversion rate was recorded at 79 μmol·cm⁻²·h⁻¹, approximately double that of pure BiVO₄, while the selectivity for glyceraldehyde reached 49%, also about twice that of pure BiVO₄. The incorporation of Mo has been shown to enhance the stability of the BiVO₄. Additionally, Mo doping improves the efficiency of electron-hole transport and increases the carrier concentration within the BiVO₄. This enhancement leads to a greater number of holes participating in the formation of iron oxyhydroxide (FeOOH), thereby stabilizing the FeOOH co-catalyst within the glycerol conversion system. The FeOOH co-catalyst facilitates the adsorption and oxidation of the primary hydroxyl group of glycerol, resulting in the cleavage of the C−H bond to generate a carbon radical (C). The interaction between the carbon radical and the hydroxyl group produces an intermediate, which subsequently dehydrates to form glyceraldehyde (GLAD). Full article

The biomass-to-liquid process is a promising alternative for sustainably meeting the growing demand for liquid fuels. This study focuses on the fabrication, characterization, and performance of a structured iron catalyst for producing hydrocarbons through Fischer–Tropsch synthesis (FTS). The catalyst was designed to address some drawbacks of conventional supported catalysts, such as low utilization, poor activity, and instability. The experimental investigation involved the manufacturing and characterization of both promoted and unpromoted iron-based catalysts. The performance of the structured iron catalyst was assessed in a fixed-bed reactor under relevant industrial conditions. Notably, the best results were achieved with a syngas ratio typical of the gasification of lignocellulosic biomass, where the catalyst exhibited superior catalytic activity and selectivity toward desired hydrocarbon products, including light olefins and long-chain paraffins. The resulting structured catalyst achieved up to 95% CO conversion in a single pass with 5% selectivity for CH₄. The results indicate that the developed structured iron catalyst has considerable potential for efficient and sustainable hydrocarbon production via the Fischer–Tropsch synthesis. The catalyst’s performance, enhanced stability, and selectivity present promising opportunities for its application in large-scale hydrocarbon synthesis processes. Full article

This study discloses the noncovalent immobilization of a bienzyme cascade composed of glucose oxidase (GOx) and horseradish peroxidase (HRP) onto magnetically responsive polyamide microparticles (PA MPs). Porous PA6, PA4, and PA12 MPs containing iron fillers were synthesized via activated anionic ring-opening polymerization in suspension, alongside neat PA6 MPs used as a reference. Four hybrid catalytic systems (GOx/HRP@PA) were prepared through sequential adsorption of HRP and GOx onto the various PA MP supports. The initial morphologies of the supports and the hybrid biocatalysts were characterized by SEM, followed by evaluation of the catalytic performance using a two-step glucose oxidation cascade process. Among all systems, the GOx/HRP@PA4-Fe complex exhibited the highest activity, being approximately 1.5 times greater than the native enzyme dyad, followed by the PA6-supported system with slightly inferior performance. All systems obeyed Michaelis–Menten kinetics, with the immobilized cascades displaying higher Kₘ and Vₘₐₓ values than the non-immobilized enzyme pair while maintaining comparable catalytic efficiencies, CE (CE = k_cat/Kₘ). Subsequently, the immobilized and native enzyme systems were employed for the polymerization of aniline. According to UV–VIS, complete monomer conversion was achieved within 24 h for selected catalysts, and FTIR analysis confirmed the formation of polyaniline in the emeraldine base form without the use of template molecules. These findings highlight the potential of Fe-containing polyamide microparticles as efficient supports for the sustainable, enzyme-mediated synthesis of intrinsically conductive aromatic polymers. Full article

In this study, the degradation of Nile Blue dye was investigated using homogeneous and heterogeneous photocatalytic methods based on the photo-Fenton reaction. More specifically, for homogeneous photocatalysis, the classical photo-Fenton (UV/Fe²⁺/H₂O₂) and modified photo-Fenton-like (UV/Fe²⁺/S₂O₈²⁻) systems were studied, while for heterogeneous photocatalysis, a commercial MOF catalyst, Basolite F300, and a natural ferrous mineral, geothite, were employed. Various parameters—including the concentrations of the oxidant and catalyst, UV radiation, and pH—were investigated to determine their influence on the reaction rate. In homogeneous systems, an increase in iron concentration led to an enhanced degradation rate of the target compound. Similarly, increasing the oxidant concentration accelerated the reaction rate up to an optimal level, beyond which radical scavenging effects were observed, reducing the overall efficiency. In contrast, heterogeneous systems exhibited negligible degradation in the absence of an oxidant; however, the addition of oxidants significantly improved the process efficiency. Among the tested processes, homogeneous techniques demonstrated a superior efficiency, with the conventional photo-Fenton process achieving complete mineralization within three hours. Kinetic analysis revealed pseudo-first-order behavior, with rate constants ranging from 0.012 to 0.688 min⁻¹ and correlation coefficients (R²) consistently above 0.90, confirming the reliability of the applied model under various experimental conditions. Nevertheless, heterogeneous techniques, despite their lower degradation rates, also achieved high removal efficiencies while offering the advantage of operating at a neutral pH without the need for acidification. Full article

Sulfamethazine (SMT) is an antibiotic with good antimicrobial effect and is widely used to treat human and livestock diseases. Though the degradation of SMT by the conventional Fenton and electro-Fenton (EF) processes is efficient, it is limited by a narrow pH and iron sludge generation. Herein, we constructed a cost-effective EF system with the synergistic effect of zero-valent iron (Fe⁰) and sulfite (Fe⁰-EF/Sulfite), and key parameters such as applied current, catalyst dosing, sulfite dosage, and initial pH were optimized. Under the optimal conditions (Fe⁰ dosing of 50 mg/L, sulfite dosage of 1.5 mM, current of 40 mA, and pH of 3), the removal efficiency of 10 mg/L SMT reached 100% within 30 min, and the degradation rate constant reached 0.194 min⁻¹. Electron paramagnetic resonance (EPR) analysis and quenching experiments confirmed the generation of various reactive oxygen species (ROS), such as ^•OH, SO₄⁻, O₂⁻, and ¹O₂, which significantly improved the pollutant removal efficiency. Sulfite accelerated iron cycling and inhibited the formation of iron sludge, thus broadening the pH range of the reaction from three to eight and overcoming the limitations of the conventional EF process. The Fe⁰-EF/Sulfite system performs cost-effectively at a wide pH range, providing an efficient and low-carbon solution for environmental pollution remediation with broad application prospects. Full article

The aim of this work was the preparation of ceramic monolithic catalysts for the catalytic oxidation of gaseous mixture of benzene, toluene, ethylbenzene and o-xylene BTEX. The possibility of using zirconium dioxide (ZrO₂) as a filament for the fabrication of 3D-printed ceramic monolithic carriers was investigated using fused filament fabrication. A mixed manganese and iron oxide, MnFeO_x, was used as the catalytically active layer, which was applied to the monolithic substrate by wet impregnation. The approximate geometric surface area of the obtained carrier was determined to be 53.4 cm², while the mass of the applied catalytically active layer was 50.3 mg. The activity of the prepared monolithic catalysts for the oxidation of BTEX was tested at different temperatures and space times. The results obtained were compared with those obtained with commercial monolithic catalysts made of ceramic cordierite with different channel dimensions, and with monolithic catalysts prepared by stereolithography. In the last part of the work, a kinetic analysis and the modeling of the monolithic reactor were carried out, comparing the experimental results with the theoretical results obtained with the 1D pseudo-homogeneous and 1D heterogeneous models. Although both models could describe the investigated experimental system very well, the 1D heterogeneous model is preferable, as it takes into account the heterogeneity of the reaction system and therefore provides a more realistic description. Full article

The efficient simultaneous removal of NO_x and CO from sintering flue gas under low-temperature conditions (110–180 °C) in iron and steel enterprises remains a significant challenge in the field of environmental catalysis. In this study, we present an innovative strategy to enhance the performance of CuSmTi catalysts through silver modification, yielding a bifunctional system capable of oxygen structure regulation and demonstrating superior activity for the combined NH₃-SCR and CO oxidation reactions under low-temperature, oxygen-rich conditions. The modified AgCuSmTi catalyst achieves complete NO conversion at 150 °C, representing a 50 °C reduction compared to the unmodified CuSmTi catalyst (T_100% = 200 °C). Moreover, the catalyst exhibits over 90% N₂ selectivity across a broad temperature range of 150–300 °C, while achieving full CO oxidation at 175 °C. A series of characterization techniques, including XRD, Raman spectroscopy, N₂ adsorption, XPS, and O₂-TPD, were employed to elucidate the Ag-Cu interaction. These modifications effectively optimize the surface physical structure, modulate the distribution of acid sites, increase the proportion of Lewis acid sites, and enhance the activity of lattice oxygen species. As a result, they effectively promote the adsorption and activation of reactants, as well as electron transfer between active species, thereby significantly enhancing the low-temperature performance of the catalyst. Furthermore, in situ DRIFTS investigations reveal the reaction mechanisms involved in NH₃-SCR and CO oxidation over the Ag-modified CuSmTi catalyst. The NH₃-SCR process predominantly follows the L-H mechanism, with partial contribution from the E-R mechanism, whereas CO oxidation proceeds via the MvK mechanism. This work demonstrates that Ag modification is an effective approach for enhancing the low-temperature performance of CuSmTi-based catalysts, offering a promising technical solution for the simultaneous control of NO_x and CO emissions in industrial flue gases. Full article

The sludge produced by the Fenton process contains mixed-valence iron particulates (hereafter called Fenton wastes). Using a solvothermal method, we fabricated a new heterogeneous photo-Fenton catalyst using Fenton wastes and metal–organic frameworks (MOFs). Nanoporous metal carboxylate (MIL-88) MOF impregnated with Fenton waste was functionalized using 2,5-dihydroxyterephthalic acid (x-HO-MIL-88-C, x, concentration of the 2,5-dihydroxyterephthalic acid). The efficiency of x-HO-MIL-88-C was examined under visible light radiation using methylene blue (MB) as an index pollutant. We observed the best catalytic performance for MB degradation by 4-HO-MIL-88-C. In the photo-Fenton process, the simultaneous presence of singlet oxygen, superoxide, and hydroxyl radicals is confirmed by free radical quenching and electron spin resonance spectral data. These free radicals associate with holes in the non-selective degradation of MB. The 4-HO-MIL-88-C catalyst shows good stability and reusability, maintaining over 80% efficiency at the end of five consecutive cycles. This work opens up a new path for recycling Fenton wastes into usable products. Full article