Search Results (1,009)

With changes in the global energy structure, ammonia has emerged as a favorable hydrogen storage medium due to its excellent properties. This work details the synthesis of a barium-doped cobalt–iron alloy catalyst via subsequent heat treatment. This alloy efficiently catalyzes the decomposition of ammonia into hydrogen. The results showed that using characterization methods such as TEM and XRD indicated that adding Ba to this system could regulate the microstructure of the Co-Fe alloy. After calcination, the barium promoted a reduction in the particle size of Co-Fe nanoparticles, enabling their uniform dispersion on the surface and a more uniform dispersion and improving the accessibility of the exposed surface. The optimized catalyst (0.05Ba-0.25CoFe/CeO₂) achieved an ammonia conversion of 93.2% at 550 °C under a gas hourly space velocity of 30,000 mL·g_cat⁻¹·h⁻¹. Mechanistic analysis based on XPS and CO₂-TPD results indicated that the barium optimized the electronic structure and alkaline sites of Co-Fe, promoted the desorption of nitrogen, and thereby accelerated the reaction kinetics of ammonia decomposition. This research provides a strategic method and theoretical basis for designing high-performance non-precious metal catalysts for ammonia decomposition. Full article

We report the synthesis of Fe/N/C ORR electrocatalysts by an original collinear CO₂ laser pyrolysis of liquid aerosol droplets in various configurations and compared them to a catalyst synthesized in the classical perpendicular one. While the precursors were always injected at the bottom side of the reactor, two collinear configurations of the laser entry into the reactor are considered: by the Top Side (T.S.) or by the Bottom Side (B.S.). The two corresponding catalysts sets show significant different ORR performances. An in-depth XPS analysis and fitting of the N1s spectra allowed for drawing the ORR performance as a function of FeN_x sites components. An original approach considering the energy delivered to a quantity of precursors in J.g⁻¹, linked to the flame temperature feature, evidenced very different conditions for perpendicular CO₂ laser pyrolysis and each of the two collinear configurations. This mass-weighted energy delivered in the classical perpendicular configuration is too low to allow for the formation of FeN_x sites and the resulting ORR performance is extremely poor, suggesting a marginal role of nitrogen species without interaction with iron atoms. In contrast, the delivered mass-weighted energies are sufficient in both collinear configurations to produce FeN_x sites. The ORR performance for catalysts produced in these both configurations is positively correlated with the amount of energy deposited on the precursors. The ORR performance in the T.S. laser configuration is positively correlated to the amount of FeN_x sites. The best performing catalysts obtained in the B.S. configuration show an opposite variation. These trends, and the ORR performance degradation of B.S. catalysts under prolonged chronoamperometry are discussed in light of the effect of temperature on the formation of the various kind of FeN_x sites. A tentative explanation is given, considering that N1s XPS fitting with a single FeN_x component may hinder the fact that Pyridinic sites components may contain a part of FeN_x sites, as suggested by theoretical calculation from the literature. The best catalysts obtained in this work by collinear configuration show similar performances to those obtained by double stage perpendicular pyrolysis previously reported with an ORR onset potential of ~860 mV. Full article

Advanced oxidation processes based on photo-Fenton chemistry have gained increasing attention as effective treatment alternatives for the removal of pharmaceutical contaminants from water and wastewater systems. However, large-scale implementation remains constrained by operational requirements, limited mineralization efficiency, and challenges associated with process stability and selectivity. This review provides a critical assessment of recent advances (2022–2025) in conventional photo-Fenton and hybrid systems, including photocatalysis/photo-Fenton and sono-photo-Fenton processes, with emphasis on their performance in water and wastewater treatment applications. The removal of non-steroidal anti-inflammatory drugs, antibiotics, pharmaceutical mixtures, and real wastewater matrices is analyzed considering catalyst configuration, irradiation sources, oxidant utilization, and operating conditions relevant to practical treatment scenarios. Conventional homogeneous Fe²⁺/H₂O₂ systems enable rapid contaminant degradation but typically require acidic conditions and show limited mineralization efficiency. In contrast, iron-complexed and heterogeneous catalysts allow operation under near-neutral pH and visible-light irradiation, improving applicability in realistic water treatment systems. Hybrid photocatalysis/photo-Fenton processes enhance treatment efficiency through synergistic generation of reactive oxygen species, while ultrasound-assisted systems further intensify oxidation rates and contaminant removal. Special attention is given to oxidation mechanisms, catalyst stability, transformation products, and toxicity evolution to identify the key factors controlling treatment performance. Finally, current technological limitations, operational challenges, and design considerations for process integration, scale-up, and sustainable implementation in water and wastewater treatment are discussed. Full article

Carbon dioxide (CO₂) capture is a cornerstone of global carbon neutrality, yet the high energy penalty associated with solvent regeneration—particularly for monoethanolamine (MEA) systems—remains a major barrier to its sustainable deployment. This study presents a sustainable and high-performance catalytic solution using micro-sized iron oxyhydroxide (β-FeOOH). Characterized by a high specific surface area ($287 m²/g) and a synergistic distribution of abundant Lewis and Brønsted acid sites, the β-FeOOH catalyst significantly enhances CO₂ desorption kinetics. Experimental results demonstrate that the incorporation of β-FeOOH into a 30 wt% MEA solution increases the CO₂ desorption rate by 10.9% while simultaneously lowering the regeneration temperature from the conventional 120 °C to 85 °C. Such a reduction in thermal requirements offers a pathway to utilize low-grade industrial waste heat, drastically improving the process’s energy efficiency. Furthermore, the catalyst exhibited remarkable cyclic stability over ten consecutive cycles, maintaining its structural integrity and catalytic activity. These findings highlight β-FeOOH as an eco-friendly, cost-effective, and robust catalyst that aligns with the principles of green chemical engineering, offering a scalable strategy to enhance the sustainability of carbon capture operations. Full article

Achieving selective conversion of lignin-derived phenolic compounds to cycloalkanes under mild conditions remains a significant challenge. Herein, we report a novel iron-incorporated two-dimensional NiO nanosheet supported Pd-Pt alloy catalyst (Pd_1.7-Pt_0.3/NiO-5FeO_x) that is capable of facilitating highly efficient hydrodeoxygenation (HDO) of lignin-derived phenolic model compounds (e.g., 2,6-dimethoxy-4-methylphenol) under mild conditions (250 °C, 5 atm H₂). The reaction mechanism was investigated through various characterization techniques and mechanistic studies: introducing FeO_x into the NiO support increases the proportion of defect-related oxygen species (Oβ), enhances adsorption of the key hydrogenated alcohol intermediate 4-methylcyclohexanol, and optimizes the acidity distribution of the catalyst, thereby promoting C(_sp³)-O bond cleavage (dehydroxylation) toward cycloalkane formation. The catalyst achieved high conversion (>95%) for various lignin-derived phenolics and high selectivity (93.0%) toward methylcyclohexane under mild conditions. This work offers new insights into the design of efficient biomass conversion catalysts under mild conditions and provides an energy-efficient route for the sustainable utilization of lignin resources. Full article

Bentonite-supported iron catalysts (Bent-Fe) were synthesized and investigated for their application in the heterogeneous electro-Fenton process for amoxicillin (AMX) degradation. The synthesized catalyst was thoroughly characterized using BET, XRD and SEM-EDS analyses, which confirmed the successful incorporation and homogeneous distribution of iron within the bentonite matrix. Acid activation significantly increased the specific surface area from 32 to 216 m² g⁻¹, while subsequent iron impregnation reduced it to 152 m² g⁻¹, indicating effective iron immobilization within the porous structure. High-resolution XPS analysis of Bent-Fe indicates that the Fe(III) is embedded within the bentonite matrix. These results confirm the successful formation of the Fe(III)-bentonite catalyst, in which both components retain their structural integrity. Adsorption experiments showed that AMX adsorption onto Bent-Fe was negligible over the investigated pH range. Despite this limited adsorption, the electro-Fenton/Bent-Fe system exhibited high degradation efficiencies reaching 95% at pH 3 and 91% at pH 6 after 120 min of electrolysis. These degradation rates corresponded to chemical oxygen demand (COD) removals of 55% and 39%, respectively. The comparable performance near-neutral pH conditions demonstrates the feasibility of operating the heterogeneous electro-Fenton process at near-neutral pH conditions, highlighting the effectiveness of bentonite as a support material for iron stabilization and catalytic degradation of AMX. Full article

The hematite phase decorated with iron-doped cerium oxide nanoparticles (F@FC) was precipitated from cerium and iron oxalate intermediate products. The photocatalytic composite of graphitic carbon nitride (gCN) and F@FC was prepared by a simple method involving mixing the two components, followed by thermal treatment at 400 °C. According to electron microscopy, F@FC is composed of a submicron iron oxide (hematite) phase decorated with iron-doped cerium oxide nanoparticles deposited on gCN substrate. A hierarchically structured composite was observed instead of a simple mechanical mixture of α-Fe₂O₃, Fe-CeO₂, and gCN. To observe two types of degradation activity, photocatalytic and Photo-Fenton degradation activity, Rhodamine B (RhB) was applied as the model water pollutant. The influence of the amount of photocatalyst, the RhB concentration, the presence of cations and anions, the pH, and the effect of e⁻, h⁺, •OH, and •O₂⁻ scavenging reactants were studied. The Photo-Fenton degradation exhibited high efficiency across the entire tested pH range, whereas photocatalytic degradation showed comparable activity only at acidic pH. The F@FC-gCN composite catalyst exhibited a high degree of recyclability. The degradation pathways of photocatalytic and Photo-Fenton reactions were suggested by HPLC-MS analysis of the reaction products. A notable finding of this study was the observation that the green-yellow, fluorescent intermediate Rhodamine 110 was formed during the photocatalytic degradation of RhB. However, the high reactivity of the generated •OH radicals during Photo-Fenton degradation has been demonstrated to inhibit the formation of intermediate Rhodamine 110. Full article

The oxygen evolution reaction (OER), a key half-reaction in electrochemical water splitting, is limited by sluggish multi-electron transfer kinetics, starting extensive research into efficient, low-cost nanoscale electrocatalysts, particularly those based on nickel, cobalt, and iron, as well as mixed-metal, hybrid, and heteroatom-doped carbon-based metal-free systems, as presented here. Ni- and Co-based electrocatalysts show high efficiency for alkaline OER due to optimized nanostructures, surface modifications, heterostructure design, and multi-metal doping, which enhance activity, stability, and electronic properties. Their performance relies on precise atomic-level control of structure and synergistic interactions, enabling them to approach or rival noble-metal catalysts. Iron-based electrocatalysts are also promising due to their abundance, low cost, and flexible redox chemistry, forming active iron oxyhydroxide species during operation; however, their low conductivity requires structural and electronic optimization. Beyond Fe, Ni, and Co, copper-based compounds, zeolitic imidazolate framework-derived structures, and manganese phosphide–cerium oxide composites offer enhanced oxygen vacancies, tunable structures, and strong interfacial synergy. Furthermore, heteroatom-doped carbon materials incorporating nitrogen, phosphorus, or sulfur improve catalytic activity by modifying electronic structure, creating active sites, and enhancing charge transfer. Overall, careful control of composition, structure, and electronic properties enables the development of efficient, durable, and scalable noble-metal-free catalysts for OER. Full article

The thermal decomposition (pyrolysis) of polypropylene has been investigated as a viable method for polymer waste recycling and the production of hydrogen-rich fuel. This study examined the effects of atmosphere, temperature, and catalytic systems based on iron oxide and strontium titanate, with a focus on gas-phase composition and reaction dynamics. A reactor geometry conducive to in-bed reforming was utilized, leading to a purer gas output compared to commonly reported results, making it suitable for solid oxide fuel cell (SOFC) applications. The hydrogen concentration was enhanced with increasing temperature, primarily due to the intensified reforming of methane and higher hydrocarbons. However, only marginal improvements were observed between 700 °C and 800 °C, which limits the benefits of higher energy input. The introduction of small amounts of water vapor (approximately 3% relative humidity) resulted in a reduction in solid residue formation by approximately 50% and a slight increase in hydrogen yield. Conversely, CO₂ atmospheres suppressed hydrogen production and increased residual solids but allowed for better control over reaction dynamics. The combined strontium titanate iron oxide catalyst (S-STO@Fe_xO_γ) demonstrated high efficacy, reducing solid residues to nearly zero and producing gas mixtures containing up to 45% hydrogen. This indicates significant potential for application and further development. These findings underscore the feasibility of in-bed reforming in polypropylene pyrolysis as a waste-to-energy strategy for hydrogen-rich fuel production, warranting further optimization and investigation for SOFC integration. Full article

CO₂-assisted catalytic pyrolysis presents a viable and promising approach to addressing plastic waste pollution and mitigating climate change. However, the effects of the metal–catalyst combination mode and the spatial distance between metal–acid sites on catalytic performance remain unclear. In this study, the reaction behaviors of the configurations, Fe₃O₄ and ZSM-5 in tandem catalysis (Fe₃O₄&HZ), their physical mixture (Fe₃O₄-HZ), and Fe-loaded ZSM-5 (Fe/HZ), were compared in polypropylene pyrolysis under a CO₂ atmosphere. The aromatic contents followed this order: Fe/HZ > Fe₃O₄-HZ > Fe₃O₄&HZ > ZSM-5 > Fe₃O₄. Specifically, Fe/HZ with the highest degree of metal–zeolite proximity achieved an aromatic content of 66.1%, significantly higher than the 34.2% obtained with Fe₃O₄&HZ, demonstrating that closer metal–acid proximity promoted aromatic formation. Moreover, Fe/HZ significantly reduced coke deposition. Based on characterization results from XRD, SEM, TEM, XPS, and NH₃-TPD, the enhanced spatial proximity between metal and acid sites strengthened the functional synergy between iron-based redox sites and zeolitic Brønsted acid sites. This synergy facilitated the reverse water–gas shift reaction of CO₂, which consumed hydrogen generated during aromatization and shifted the reaction equilibrium toward enhanced aromatic production. These findings would offer theoretical and strategic insights into the optimization of CO₂-assisted catalytic pyrolysis systems for the sustainable upcycling of plastic waste. Full article

Anilido-oxazoline iron(II) chloride complexes were synthesized and evaluated for their catalytic performance in the ring-opening polymerization (ROP) of cyclic esters. Complexes 1–5 were obtained via transmetalation of FeCl₂(THF)_1.5 and pyridine derivatives with in situ generated anilido-oxazoline lithium. They exhibited excellent controllability and high initiating efficiency in the ROP of ε-caprolactone (CL). In the presence of benzyl alcohol as the initiator, these iron complexes efficiently catalyzed the ROP of CL, reaching a TOF of 3.2 × 10³ h⁻¹. High molecular weight polycaprolactone was obtained with a number-average molecular weight of 161.38 kg/mol. The chain initiation and propagation processes were investigated using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and kinetic analyses. Kinetic studies confirmed a pseudo-first-order dependence of the polymerization rate on catalyst concentration. Furthermore, the iron(II) complexes were also found to be efficient catalysts for the ROP of δ-valerolactone. Full article

Iron(II) and manganese(II) complexes with N4Py [N4Py—N,N-bis(2-pyridylmethyl)-N-(bis-2-pyridylmethyl)amine] have been found to activate O₂ for the oxidation of α-pinene in acetonitrile. For example, for 1 M α-pinene, 0.5 mM [(N4Py)Fe^II]²⁺, and dioxygen as an oxidant, 90 mM α-pinene epoxide, 48 mM verbenol, and 50 mM verbenone have been formed, which, taking into account the concentrations of the minor products (myrtenol and myrtenal), gives a turnover number approximately equal to 400. Based on the amounts of products formed, the conversion of α-pinene is approximately 20% and 18% for iron and manganese catalysts, respectively. Although the manganese catalyst is somewhat less effective than the iron catalyst, the selectivity of the products is similar for both catalysts. Replacement of dioxygen with air as the oxidant causes the reaction yield to be lower. The proposed mechanism assumes the formation of a metal(IV)-oxo complex [(N4Py)M^IV=O]²⁺, M–Fe or Mn, during the simultaneous combination of a catalyst, O₂, and substrate, and its subsequent reactions toward the observed products. Full article

Catalytic biomass gasification is considered a promising route for the production of hydrogen-rich syngas. However, the impact of catalytic enhancement on gas composition is a complex phenomenon, as experimental outcomes are often strongly dependent on reactor configurations and kinetic effects. To address these challenges, a thermodynamic equilibrium-based modeling approach was developed to theoretically investigate the influence of catalytic enhancement in biomass steam gasification. The gasification process was modeled using Gibbs free energy minimization, focusing on the elemental composition of biomass and the equilibrium distribution among the major gaseous species, namely H₂, CO, CO₂, CH₄, and H₂O. The effects of the different catalyst types, including dolomite, Ni/olivine, and iron-based catalysts, were examined through catalyst-dependent activity coefficients. Simulations were carried out under steam gasification conditions at atmospheric pressure, with particular emphasis on the influence of temperature, steam-to-biomass ratio, and catalyst activity on syngas composition. The results showed that increasing catalyst activity enhanced hydrogen production while suppressing methane formation, primarily through intensified tar reforming and water–gas shift reactions. The model successfully reproduced widely accepted thermodynamic trends reported in the literature. Overall, the proposed framework can provide a flexible and computationally efficient screening-level tool for the theoretical assessment of catalytic effects in biomass gasification, offering valuable insights for preliminary catalyst selection and conceptual process design. Full article

Linear α-olefins (LAOs) from CO/H₂ represent an attractive non-petroleum route, yet their selective formation over Fe catalysts is often limited by CO₂ formation via water–gas shift (WGS) reaction and by secondary hydrogenation that consumes terminal olefins. In this work, we demonstrate that these competing pathways can be regulated on carbon-nanotube (CNT) supported Fe catalysts by controlling the CNT interfacial oxygen environment through NO treatment or high-temperature annealing and by adjusting the Mn incorporation protocol between co-impregnation and stepwise addition. Under identical reaction conditions at 280 °C and 3.0 MPa with an H₂-to-CO ratio of 1, high-temperature treated CNTs improve olefin preservation and LAO retention compared with NO-treated CNTs. Mn promotion further shifts selectivity toward α-olefins and lowers CO₂ selectivity. At the same Fe-to-Mn ratio, the Mn introduction sequence produces distinct reducibility and CO-binding behaviors that lead to different steady-state oxide and carbide phases. XPS, H₂-TPR, and CO-TPD collectively suggest that CNT pretreatment and the Mn protocol modulate near-surface oxygen speciation, reduction kinetics, and CO adsorption strength. Mössbauer spectroscopy confirms a predominantly χ-Fe₅C₂ population and indicates the presence of ε-Fe₂C in selected samples together with residual oxide and superparamagnetic Fe species. These results highlight the importance of controlling the CNT–metal interface and Mn–Fe proximity to enhance LAO retention under high-temperature CO hydrogenation. Full article

Pyrolysis of plastic from waste electrical and electronic equipment (WEEE) is a promising method for producing value-added chemicals. However, flame retardants in WEEE can cause halogen contamination in pyrolysis oil, reducing its value. This work aims to develop an innovative catalytic hydrodehalogenation (CHD) protocol for the removal of chlorobenzene and bromobenzene. Iron sulphate heptahydrate (FeSO₄·7H₂O) and nickel ammonium sulphate hexahydrate ((NH₄)₂Ni(SO₄)₂·6H₂O) were used as catalysts, while sodium borohydride (NaBH₄) acted as a hydrogen donor for iron reduction. The novelty of the process lies in the generation of nano zero-valent iron (nZVI) that takes place within the CHD reactor (in situ) without the addition of strong acids. Various experimental set-ups were investigated to optimise the key process parameters (e.g., reagent concentrations). The optimal conditions—obtained in the autoclave at 30 °C with a 1:1 molar ratio of chlorobenzene to catalyst, omission of nickel salt, and 5 mmol of NaBH₄—resulted in a 75% reduction in chlorobenzene and complete removal of bromobenzene. The results confirm the effectiveness of the proposed protocol for the dehalogenation of chlorobenzene and bromobenzene, which can facilitate the valorization of pyrolysis oils derived from plastic waste, contributing to the closure of the WEEE cycle (the widest and fastest-growing source of global waste with significant environmental, social and economic impacts). Full article