Search Results (1,245)

Constructed wetlands (CWs) are signified as green, self-sustaining systems for wastewater treatment. To date, their conventional designs struggle with slow kinetics and poor removal of refractory pollutants. This review redefines CWs as photo-reactive engineered systems, integrating near-neutral Fenton and photo-Fenton processes and in-situ oxidant generation to overcome diffusion limits, acid dosing, and sludge formation. By coupling catalytic fillers, solar utilization, and plant–microbe–radical (ROS) synergies, the approach enables intensified pollutant degradation while preserving the low-energy nature of CWs. Bibliometric trends indicate a sharp rise in studies linking CWs with advanced oxidation and renewable energy integration, confirming the emergence of a circular treatment paradigm. A decision framework is proposed that aligns material selection, reactor hydrodynamics, and solar light management with sustainability indicators such as energy efficiency, Fe-leach budget, and ROS-to-photon yield. This synthesis bridges environmental biotechnology with solar-driven catalysis, paving the way for next-generation eco-engineered wetlands capable of operating efficiently beyond the classical Fenton constraints. This work introduces the concept of “Constructed Wetlands Beyond the Fenton Limit”, where CWs are reimagined as photo-reactive circular systems that unify catalytic, biological, and solar processes under near-neutral conditions. It provides the first integrated decision matrix and performance metrics connecting catalyst design, ROS efficiency, and circular sustainability that offers a scalable blueprint for real-world hybrid wetland applications. Full article

This study takes a further step forward in the analytical treatment of Langmuir–Hinshelwood (LH) kinetics for heterogeneous catalysis by deriving its closed-form solution. Unlike previous studies, we present a general solution that does not impose severe restrictions on the experimental conditions. This solution not only recovers the typical first- and zeroth-order regimes but also enables the simultaneous determination of the reaction rate constant and absorption–desorption equilibrium constant, unlike the traditional approaches to this equation, which needed additional isotherm experiments. The final solution requires a fine mathematical treatment for its numerical implementation, but enhanced approximations of the closed-form solution overcome this problem without losing the main advantage of calculating both constants at the same time. A parameter called “critical time” has been introduced, whose calculation allows us to distinguish quantitatively between kinetic regimes. Finally, the validation of these approximations has been carried out with experiments on zinc oxide and anatase (TiO₂) under different conditions. Anatase experiments undoubtedly show a first-order tendency, regardless the quantity of powder. On the other hand, the degradation regime of the ZnO case cannot be easily ascribed to the zeroth or first order by simple inspection, but the model can mathematically rule out the zeroth order and confirm that it undergoes first-order degradation. Full article

The Electro-Fenton (EF) process is a promising technology for the sustainable remediation of organic contaminants in complex wastewater. In this study, a weak magnetic field (~150 G) was applied to enhance the performance of an EF system using magnetite (Fe₃O₄) synthesized by a controlled co-precipitation route as a recyclable solid iron source. The magnetite was characterized by FTIR, SEM/EDS, and XPS, confirming the coexistence of Fe²⁺/Fe³⁺ species essential for in situ Fenton-like reactions. Under the selected operating conditions (90 min reaction time), magnetic-field assistance improved methylene blue decolorization from 14.2% to 46.0% at pH 3. FeSO₄ was used only as a homogeneous benchmark, whereas the magnetite-based system operated without soluble iron addition, minimizing sludge formation and secondary contamination. These results demonstrate the potential of magnetite-assisted and magnetically enhanced EF systems as a low-cost, sustainable alternative for the treatment of dye-containing industrial wastewater and other complex effluents. Full article

The escalating global water crisis demands the development of cost-effective and environmentally sustainable treatment technologies. Among various advanced oxidation processes (AOPs), peracetic acid (PAA) has emerged as a promising oxidant, owing to its high redox potential, chemical stability, and potent disinfection capability. Nevertheless, the lack of highly efficient catalysts remains a major obstacle to achieving the effective degradation of contaminants of emerging concern in wastewater. Heterogeneous catalysis has proven to be a viable strategy for enhancing PAA activation, highlighting the urgent need for catalysts with superior activity, stability, and recyclability. Metal–organic frameworks (MOFs), with their large surface areas, tunable porosity, and structural diversity, provide versatile platforms for catalyst design. Recently, MOF-derived materials have attracted increasing attention for PAA activation, offering a new frontier in advanced oxidation technologies for efficient and sustainable wastewater remediation. This review systematically examines the role of MOFs in PAA activation, from pristine frameworks to MOF-based composites and MOF-derived catalysts. Mechanistic insights into PAA activation are highlighted, strategies for engineering MOF-based composites with synergistic catalytic properties are discussed, and the transformation of MOFs into robust derivatives with improved stability and reactivity is explored. Special attention is given to the identification and quantification of reactive species generated in PAA systems, providing a critical understanding of reaction pathways and catalytic performance. Finally, current challenges and future directions are outlined for designing highly efficient, recyclable, and environmentally compatible MOF-based catalysts, emphasizing their potential to significantly advance PAA-based AOPs. Full article

The development of a metalloenzyme-like catalytic system for the efficient oxidation of olefins under a dioxygen (O₂) atmosphere at room temperature is of significant interest in the field of catalysis. Herein, we present a highly active and selective aerobic epoxidation of olefins using metalloenzyme-like catalysts based on a non-heme ligand, tris(2-pyridylmethyl)amine (TPA). Notably, manganese chloride complexed with TPA (Mn(TPA)Cl₂) demonstrated excellent activity for the epoxidation of trans-stilbene using O₂ as the oxidant in the presence of a co-reductant at 30 °C. A quantitative conversion of 99% and high yield of 98%, as determined by gas chromatography using an external standard method, were achieved under optimum reaction conditions. Furthermore, Mn(TPA)Cl₂ exhibited a good substrate tolerance to styrene derivatives with electron-withdrawing or electron-donating groups, cyclic olefins with different substituents and substitution degrees, as well as long-chain olefins. Coupled with a high turnover frequency (TOF) of up to 30,720 h⁻¹, these results underscore the potential of Mn(TPA)Cl₂ as a promising metalloenzyme-like catalytic platform for the aerobic synthesis of diverse epoxides from olefins under ambient conditions. Full article

Early oxidative stress caused by titanium implants can impair osseointegration. Manganese dioxide (MnO₂) nanozyme coatings have the potential to scavenge H₂O₂ and simultaneously generate O₂ to alleviate hypoxia, but their activity is mostly static, and the ion release is detrimental. A nano-MnO₂/Ti/P(VDF-TrFE) sandwich-structured composite was fabricated, and ferroelectric polarization was applied to preset a tunable surface potential. Kelvin probe force microscopy (KPFM) verified a presettable potential within ±500 mV. Steady-state kinetics confirmed an enhancement in overall catalytic efficiency (higher V_max and lower K_m). This translated to a faster initial decomposition rate at a low, physiologically relevant H₂O₂ concentration (300 μM). Correspondingly, under these oxidative stress conditions, cell survival in the polarized group was higher than that in the unpolarized group, indicating that the enhanced initial rate can have a positive effect in such conditions. Overall, this study demonstrates a proof-of-concept strategy to tune MnO₂ nanozyme catalysis using a polarization-preset surface potential, targeting implantation-relevant ROS-rich conditions. Full article

The formation of interfacial charge transfer (ICT) complexes between phenolic ligands and metal oxide surfaces enables surface functionalization strategies with potential applications in catalysis and bioconjugation. In this study, magnetite (Fe₃O₄) nanoparticles were modified with two phenolic ligands, 5-aminosalicylic acid (5ASA) and caffeic acid (CA), to generate ICT complexes capable of covalent or non-covalent enzyme immobilization, respectively. The modified nanomaterials were structurally characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FTIR). Horseradish peroxidase (HRP) was immobilized on these functionalized supports using varying nanoparticle amounts (10–30 mg) and initial enzyme concentrations (25–250 µg mL⁻¹). Catalytic activity was evaluated using pyrogallol oxidation assays. The Fe₃O₄/5ASA–HRP system exhibited a maximum activity of 2.5 U per 20 mg of support (approximately 125 U g⁻¹), whereas Fe₃O₄/CA showed minimal activity under the same conditions. Enzyme loading studies confirmed that 5ASA-enabled covalent attachment resulted in significantly higher immobilization efficiency (up to 1068 mg g⁻¹) compared to the CA system. Reusability tests demonstrated that the Fe₃O₄/5ASA system retained high absolute catalytic activity during the initial reaction cycles and consistently outperformed the non-covalently immobilized Fe₃O₄/CA system upon repeated reuse. The magnetic properties of Fe₃O₄ allowed rapid recovery of the biocatalysts using an external magnetic field. These results highlight the effectiveness of ICT-based functionalization for enzyme immobilization, positioning Fe₃O₄/5ASA as a promising platform for robust and reusable biocatalysts in environmental and industrial applications. Full article

The catalytic oxidation of CO is of great technological importance for the treatment of vehicle and industrial exhaust gases. PtCe-catalysts of low-temperature CO oxidation were prepared by the impregnation of ZSM-5 zeolite (Z) with aqueous solutions of H₂PtCl₆ and Ce(NO₃)₃, varying the order of metal deposition and thermal treatment conditions. The relationships between structure transformations and catalyst performance were established based on the SEM, TEM, EDX, DRIFT, and X-ray photoelectron spectroscopies data. For the Ce/Pt/Z sample, in which cerium was deposited after platinum, the 100% CO conversion temperature was only 120 °C. The inverse deposition sequence of metals (Pt/Ce/Z catalyst) resulted in CO oxidation at a higher temperature that can be decreased to 110 °C by redox treatment. The prepared catalysts were also active in the CO oxidation in excess hydrogen (PROX) but were not selective enough. However, the activity of PtCe-modified ZSM-5 enhanced greatly in the repeated cycles of CO oxidation (TOX) after testing in PROX. It is suggested that enhancing the interaction between Pt and Ce is a key factor in tuning the catalyst performance. The 0.2 wt.% Pt catalysts showed the best performance and provided complete CO conversion at 95 °C, which is a pronounced result for low-loaded Pt catalysts. Full article

ABO₃ perovskite oxides are a versatile class of materials whose surfaces and interfaces play essential roles in sustainable energy technologies, including catalysis, solid oxide fuel and electrolysis cells, thermoelectrics, and energy-relevant oxide electronics. The interplay between point defects and surface reconstructions strongly affects interfacial stability, charge transport, and catalytic activity under operating conditions. This review summarizes recent progress in understanding how oxygen vacancies, cation nonstoichiometry, and electronic defects couple to atomic-scale surface rearrangements in representative perovskite systems. We first revisit Tasker’s classification of ionic surfaces and clarify how defect chemistry provides compensation mechanisms that stabilize otherwise polar or metastable terminations. We then discuss experimental and theoretical insights into defect-mediated reconstructions on perovskite surfaces and how they influence the performance of energy conversion devices. Finally, we conclude with a perspective on design strategies that leverage defect engineering and surface control to enhance functionality in energy applications, aiming to connect fundamental surface science with practical materials solutions for the transition to sustainable energy. Full article

After being an indispensable intermediate in the oxidative exfoliation route towards graphene, graphene oxide has gained its deserved value in materials science for numerous applications, from catalysis, through energy storage and conversion, to sensor use. In this work, three graphene oxides of tuned morphology and chemistry are used as a simplified model for porous carbon materials in hydrogen storage and as a Li-ion battery anode. The BET surface areas were, respectively, 9, 13, and 535 m²/g, while the corresponding O/C values from the X-ray photoelectron spectroscopy were 0.51, 0.17, and 0.12. Additionally, the samples were thoroughly characterized using scanning and transmission electron imaging, powder X-ray diffraction, thermal stability, and Raman and Fourier transform infrared spectroscopic methods. Hydrogen adsorption isotherms (−196 °C) and their comparison with nitrogen uptake revealed that pore accessibility, porous confinement, and surface chemistry, i.e., both morphology and surface chemistry, contribute to efficient adsorption. In the anode application, by contrast, surface chemistry was the single most defining factor for performance. Full article

As one of the most intensively researched reaction systems in the field of multiphase catalysis, the technological breakthrough of CO oxidation is of great significance in addressing the health hazards and environmental pollution caused by high CO concentrations. Catalytic oxidation technology has become a core means of eliminating CO pollution due to its high efficiency and energy saving. This paper provides an in-depth analysis of various types of metal-catalyzed CO oxidation reactions and explores in detail the characteristics of the action of different mechanisms. On this basis, optimization strategies are proposed, including metal doping and controllable oxygen vacancy construction to enhance reaction selectivity and stability. In addition, the influence mechanisms of common gas components such as H₂O and SO₂ on the catalytic reaction of CO are analyzed, and targeted optimization strategies are proposed. The reaction mechanisms of CO on the metal catalyst surface are then examined. Finally, the development direction of catalysts in the field of CO deep purification is prospectively discussed, which provides theoretical support and technical routes for the construction of an efficient and stable industrialized CO oxidation system. Full article

The activation of peracetic acid (PAA) to generate highly reactive species has emerged as a promising advanced oxidation process (AOP) for the degradation of refractory organic pollutants. This review systematically summarizes the recent advancements in PAA-based AOPs, encompassing various activation strategies, underlying reaction mechanisms, and applications across different environmental matrices. The activation methods are critically discussed, including direct energy activation, homogeneous catalysis, and heterogeneous catalysis. The generation process of diverse reactive species, like hydroxyl radicals (HO·), organic radicals (CH₃C(O)O·, CH₃C(O)OO·), and singlet oxygen (¹O₂), was introduced, and their oxidation selectivity and anti-interference ability were compared. Furthermore, the practical applications of PAA-based AOPs in treating wastewater, groundwater, and contaminated soil/sediments are reviewed. Finally, this review outlines critical challenges, including potential toxic byproduct formation, catalyst stability, and economic feasibility, and proposes future research directions to facilitate the transition of PAA-based AOPs from laboratory-scale research to full-scale implementation. This review provides insights for developing efficient, selective, and sustainable oxidation technologies, thereby contributing to the mitigation of emerging contaminant threats and the advancement of environmental remediation practices. Full article

Hydrogen peroxide (H₂O₂) is a key oxidant for green chemical processes, yet its catalytic utilization and activation efficiency remain limited by material instability and uncontrolled radical release. Here, we report a dual-functional, hollow conductive polymer nanostructure that enables selective modulation of H₂O₂ reactivity through interfacial physicochemical design. Hollow polypyrrole nanospheres functionalized with carboxyl groups (PPy@PyCOOH) were synthesized via a one-step Fe²⁺/H₂O₂ oxidative copolymerization route, in which H₂O₂ simultaneously served as oxidant, template, and reactant. The resulting structure exhibits enhanced hydrophilicity, rapid redox degradability (>80% optical loss in 60 min (82.5 ± 4.1%, 95% CI: 82.5 ± 10.2%), 10 mM H₂O₂, pH 6.5), and strong electronic coupling to reactive oxygen intermediates. Subsequent tannic acid–copper (TA–Cu) coordination produced a conformal metal–polyphenol network that introduces a controllable Fenton-like catalytic interface, achieving a 50% increase in ROS yield (1.52 ± 0.08-fold vs. control, 95% CI: 1.52 ± 0.20-fold) while maintaining stable photothermal conversion under repeated NIR cycles. Mechanistic analysis reveals that interfacial TA–Cu complexes regulate charge delocalization and proton–electron transfer at the polymer–solution boundary, balancing redox catalysis with energy dissipation. This work establishes a sustainable platform for H₂O₂-driven redox and photo-thermal coupling, integrating conductive polymer chemistry with eco-friendly catalytic pathways. Full article

Gold nanoparticles (AuNPs) are promising for biomedical applications, but their synthesis often requires toxic reagents. “Green” methods utilizing biopolymers offer a sustainable alternative. This study presents a novel synthesis of stable gold nanoparticles using a disulfide-crosslinked derivative of alginic acid (AA–S–S–AA) as both a reducing agent and stabilizer. The S–S-cross-linked alginate was synthesized with a degree of substitution of ~4.2% and reacted with HAuCl₄ in water at room temperature for just 10 min to give stable and polysaccharide in situ modified gold nanoparticles (AA-AuNPs). The resulting AA-AuNPs were characterized by a surface plasmon resonance peak at 539 nm and exhibited good colloidal stability over 14 days. Electron microscopy revealed spherical nanoparticles with a bimodal size distribution (10 nm and 75–100 nm) and a visible polysaccharide shell (5–9 nm), confirming effective stabilization. X-ray photoelectron spectroscopy confirmed the presence of metallic gold (Au⁰) and Au¹⁺. NMR analysis indicated the oxidation of disulfide groups to sulfonic acid during synthesis. The nanoparticles demonstrated a high negative zeta-potential of −53.9 mV, attributable to the polyanionic alginate corona, ensuring strong electrostatic stabilization. This work establishes sulfur-modified alginic acid as an efficient platform for the rapid synthesis of stable, hybrid nanoparticles for potential use in catalysis and biomedicine. Full article

At present, various carbon materials are available as supports for metal-containing catalytic species. Carbon-based materials find application in many industrial heterogeneous catalytic processes, such as selective hydrogenation, oxidation, cross-coupling, etc. The simplicity of preparation, low cost, high stability, and the possibility of tuning surface composition and porosity cause the widespread use of metal catalysts supported on carbon materials. The surface chemistry of carbon supports plays a crucial role in catalysis, since it allows for control over the sizes of metal particles and their electronic properties. Moreover, metal-free functionalized carbonaceous materials themselves can act as catalysts. In this review, we discuss the recent progress in the field of the application of carbon supports in catalysis by metals, with a focus on the role of carbon surface functionalities and metal-support interactions in catalytic processes used in fine organic synthesis. Among carbon materials, functionalized/doped (O, N, S, P, B) activated carbons, graphenes, carbon nanotubes, graphitic carbon nitride, and carbonizates of polymers are considered supports for mono- and bimetallic nanoparticles. Full article