Search Results (11)

This study examines the solar-driven photocatalytic degradation of tetracycline hydrochloride in aqueous media using immobilized magnetite. The synthesized catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR). Photocatalytic experiments revealed that tetracycline degradation followed pseudo-first-order kinetics, achieving 48% removal within 30 min and nearly complete degradation (99%) after 120 min of solar irradiation. The addition of Fenton reagent significantly enhanced degradation efficiency by promoting the generation of reactive oxygen species. The formation of multiple degradation intermediates, along with a substantial reduction in chemical oxygen demand (COD) was observed. The immobilized magnetite catalyst exhibited good stability and reusability with minimal loss of activity over repeated cycles. Overall, the results demonstrate that magnetite-based solar photocatalysis is a cost-effective, efficient, and environmentally sustainable approach for treating TCT-contaminated wastewater. Full article

Cysteine plays a crucial role in the development of an efficient copper-catalyst system, where its thiol group serves as a strong anchoring site for metal coordination. By immobilizing copper onto cysteine-modified, polydopamine-coated magnetite particles, this advanced catalytic platform exhibits exceptional stability and catalytic activity. Chemical modification of the polydopamine (PDA) surface with cysteine enhances copper salt immobilization, leading to the formation of the Fe₃O₄@PDA-Cys@Cu platform. This system was evaluated in palladium-free, copper-catalyzed Sonogashira coupling reactions, effectively catalyzing the coupling of terminal acetylenes with aryl halides. Additionally, the Fe₃O₄@PDA-Cys@Cu platform was employed in click reactions, confirming the enhanced catalytic efficiency due to increased copper content. The reusability of the platform was further investigated, demonstrating improved performance, especially in recyclability tests in click reaction, making it a promising candidate for sustainable heterogeneous catalysis. Full article

Magnetic nanoparticles (MNPs) based on magnetite (Fe₃O₄) are attractive catalyst supports due to their high surface area, easy preparation, and facile separation, but they lack stability in acidic reaction media. The search for MNPs stable in oxidative acidic reaction media is a necessity if one wants to combine the advantages of MNPs as catalyst supports with those of iodine(III) reagents being environmentally benign oxidizers. In this work, immobilized iodophenyl organocatalysts on magnetite support (IMNPs) were obtained by crossed-linking polymerization of 4-iodostyrene with 1,4-divinylbenzene in the presence of MNPs. The obtained IMNPs were characterized by TGA, IR, SEM, STEM, and HAADF to gain information on catalyst morphology, average particle size (80–100 nm), and their core–shell structure. IMNP-catalysts tested in (i) the α-tosyloxylation of propiophenone 1 with meta-chloroperbenzoic acid (m-CPBA) and (ii) in the oxidation of 9,10-dimethoxyanthracene 3 with Oxone^® as the side-oxidant showed a similar performance as reactions using stoichiometric amounts of iodophenyl. The developed IMNPs withstand strong acidic conditions and serve as reusable organocatalysts. They are recyclable up to four times for repeated organocatalytic oxidations with rates of recovery of 80–92%. This is the first example of a—(4-iodophenyl)polystyrene shell—magnetite core-structured organocatalyst withstanding strong acidic reaction conditions. Full article

Here, we developed magnetically recoverable biocatalysts based on magnetite nanoparticles coated with an ultra-thin layer (about 0.9 nm) of chitosan (CS) ionically cross-linked by sodium tripolyphosphate (TPP). Excessive CS amounts were removed by multiple washings combined with magnetic separation. Glucose oxidase (GOx) was attached to the magnetic support via the interaction with N-hydroxysuccinimide (NHS) in the presence of carbodiimide (EDC) leading to a covalent amide bond. These steps result in the formation of the biocatalyst for D-glucose oxidation to D-gluconic acid to be used in the preparation of pharmaceuticals due to the benign character of the biocatalyst components. To choose the catalyst with the best catalytic performance, the amounts of CS, TPP, NHS, EDC, and GOx were varied. The optimal biocatalyst allowed for 100% relative catalytic activity. The immobilization of GOx and the magnetic character of the support prevents GOx and biocatalyst loss and allows for repeated use. Full article

The modified suspension polymerization technique has been used for the preparation of composite microparticles from the mixture of glycidyl methacrylate (GMA), styrene (S), and divinylbenzene (DVB) in the presence of hydrophobized Fe₃O₄ nanoparticles. The obtained polymer microspheres were characterized using different instrumental and physicochemical techniques, modified with a zero-order PAMAM dendrimer, and impregnated with palladium(II) acetate solutions to immobilize palladium(II) ions. The resulting materials were preliminarily examined as catalysts in the Suzuki reaction between 4-bromotoluene and phenylboronic acid. It was found that the addition of magnetite particles to the composition of monomers provided polymer microparticles with embedded magnetic nanoparticles. The composite microparticles obtained showed a complex, multi-hollow, or raspberry-like morphology. After their modification, they could serve as recyclable catalysts for reactions that include both 4-bromotoluene and several other aryl bromides. Full article

Catalysts play a critical role in producing most industrial chemicals and are essential to environmental remediation. Under the demands of sustainable development, environment protection, and cost-related factors, it has been suggested that catalysts are sufficiently separable and conveniently recyclable in the catalysis process. Magnetite (Fe₃O₄) nanomaterials provide a possible way to achieve this goal, due to their magnetism, chemical stability, low toxicity, economic viability, etc. Therefore, Fe₃O₄-based materials are emerging as an important solid support to load heterogeneous catalysts and immobilize homogeneous catalysts. Moreover, the addition of magnetic character to catalysts will not only make their recovery much easier but also possibly endow catalysts with desirable properties, such as magnetothermal conversion, Lewis acid, mimetic enzyme activity, and Fenton activity. The following review comprises a short survey of the most recent reports in the catalytic applications of Fe₃O₄-based magnetic materials. It contains seven sections, an introduction into the theme, applications of Fe₃O₄-based magnetic materials in environmental remediation, electrocatalysis, organic synthesis, catalytic synthesis of biodiesel, and cancer treatment, and conclusions about the reported research with perspectives for future developments. Elucidation of the functions and mechanisms of Fe₃O₄ nanoparticles (NPs) in these applications may benefit the acquisition of robust and affordable protocols, leading to catalysts with good catalytic activity and enhanced recoverability. Full article

The embedded immobilized enzymes (Rhizopus-oryzae) on the magnetic nanoparticles (Fe₃O₄-NPs) is a new application for the sustainable production of high-quality biodiesel. In this study, biodiesel is derived from Kapok oil via ultrasonication (US)-assisted catalytic transesterification method. A novel attempt is made to prepare magnetic nanoparticles embedded by an immobilized enzyme to solve the problem of enzyme denaturation. This innovative method resulted in optimum biodiesel conversion of 89 ± 1.17% under reactant molar ratio (methanol: oil) of 6:1, catalyst loading 10 wt% with a reaction time of 4 h at 60 °C. The kinetic and thermal study reveals that conversion of Kapok oil to biodiesel follows a pseudo first-order reaction kinetic with a lower ΔE of 30.79 kJ mol⁻¹. The ΔH was found to be 28.06 kJ mol⁻¹ with a corresponding ΔS of −237.12 J mol⁻¹ K⁻¹ for Fatty Acid Methyl Ester formation. The ΔG was calculated to be from 102.28 to 109.40 kJ mol⁻¹ for temperature from 313 K to 343 K. The positive value of ΔH and ΔG is an indication of endothermic and non-spontaneous reaction. A negative ΔS indicates the reactant in the transition state possesses a higher degree of ordered geometry than in its ground state. The immobilized catalysts provided great advantages towards product separation and efficient biodiesel production. Highlights: 1. Effective catalytic transesterification assisted by the ultrasonication method was used for bi-odiesel production. 2. Magnetite nanoparticles synthesized by the co-precipitation method were used as heteroge-neous catalysts. 3. An immobilized enzyme (Rhizopus-oryzae) was embedded in the heterogeneous catalyst, as it is reusable and cost-effective. 4. The maximum biodiesel yield obtained from Kapok oil was 93 ± 1.04% by catalytic trans-esterification reactions. Full article

Inorganic biopolymer-based nanocomposites are useful for stabilizing lipases for enhanced catalytic performance and easy separation. Herein, we report the operational stability, regenerability, and thermodynamics studies of the ternary biogenic silica/magnetite/graphene oxide nanocomposite (SiO₂/Fe₃O₄/GO) as a support for Candida rugosa lipase (CRL). The X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), field-electron scanning electron microscopy (FESEM), vibrating sample magnetometry (VSM), and nitrogen adsorption/desorption data on the support and biocatalyst corroborated their successful fabrication. XPS revealed the Fe₃O₄ adopted Fe²⁺ and Fe³⁺ oxidation states, while XRD data of GO yielded a peak at 2θ = 11.67°, with the SiO₂/Fe₃O₄/GO revealing a high surface area (≈261 m²/g). The fourier transform infrared (FTIR) spectra affirmed the successful fabricated supports and catalyst. The half-life and thermodynamic parameters of the superparamagnetic immobilized CRL (CRL/SiO₂/Fe₃O₄/GO) improved over the free CRL. The microwave-regenerated CRL/SiO₂/Fe₃O₄/GO (≈82%) exhibited higher catalytic activity than ultrasonic-regenerated (≈71%) ones. Lower activation ($E_a)$ and higher deactivation energies ($E_d)$ were also noted for the CRL/SiO₂/Fe₃O₄/GO (13.87 kJ/mol, 32.32 kJ/mol) than free CRL (15.26 kJ/mol, 27.60 kJ/mol). A peak at 4.28 min in the gas chromatograph-flame ionization detection (GC-FID) chromatogram of the purified ethyl valerate supported the unique six types of 14 hydrogen atoms of the ester (CAS: 539-82-2) in the proton nuclear magnetic resonance (¹H-NMR) data. The results collectively demonstrated the suitability of SiO₂/Fe₃O₄/GO in stabilizing CRL for improved operational stability and thermodynamics and permitted biocatalyst regenerability. Full article

In this work, we analyzed the suitability of a versatile recombinant lipase, secreted by Ophiostoma piceae (OPEr) and produced in Pichia pastoris, as a catalyst of the synthesis of biodiesel. The enzyme was immobilized by five covalent procedures and by hydrophobicity on functionalized nanoparticles of magnetite or of a novel Zn/Mn oxide named G1. Then, they were tested for green production of biodiesel by solventless enzymatic transesterification of discarded cooking oil and methanol (1:4) at 25 °C. The results were compared with those shown by free OPEr and the commercial lipases Eversa^® and Cal A^®. Several preparations with immobilized OPEr produced high synthesis yields (>90% transesterification), comparable to those obtained with Eversa^®, the commercial enzyme designed for this application. Three of the biocatalysts maintained their catalytic efficiency for nine cycles. The process catalyzed by AMNP-CH-OPEr was scaled from 500 µL to 25 mL (50 times), improving its efficiency. Full article

Sustainable and green synthesis of nanocomposites for degradation of pharmaceuticals was developed via immobilization and stabilization of the biological strong oxidizing agents, peroxidase enzymes, on a solid support. Sol–gel encapsulated enzyme composites were characterized using electron microscopy (TEM, SEM), atomic force microscopy, FTIR spectroscopy, and thermogravimetric analysis. Horseradish peroxidase (HRP) and lignin peroxidase (LiP) were adsorbed onto magnetite nanoparticles and sol–gel encapsulated in a surface silica layer. Encapsulation enhanced the stability of the biocatalysts over time and thermal stability. The biocatalysts showed appreciable selectivity in oxidation of the organic drinking water pollutants diclofenac, carbamazepine, and paracetamol with improved activity being pharmaceutical specific for each enzyme. In particular, sol–gel encapsulated LiP- and HRP-based nanocomposites were active over 20 consecutive cycles for 20 days at 55 °C (24 h/cycle). The stability of the sol–gel encapsulated catalysts in acidic medium was also improved compared to native enzymes. Carbamazepine and diclofenac were degraded to 68% and 64% by sol–gel LiP composites respectively at pH 5 under elevated temperature. Total destruction of carbamazepine and diclofenac was achieved at pH 3 (55 °C) within 3 days, in the case of both immobilized HRP and LiP. Using NMR spectroscopy, characterization of the drug decomposition products, and decomposition pathways by the peroxidase enzymes suggested. Full article

This study provides an overview of the environmental impacts associated with the production of different magnetic nanoparticles (NPs) based on magnetite (Fe₃O₄), with a potential use as heterogeneous Fenton or photo-Fenton catalysts in wastewater treatment applications. The tendency of Fe₃O₄ NPs to form aggregates in water makes necessary their decoration with stabilizing agents, in order to increase their catalytic activity. Different stabilizing agents were considered in this study: poly(acrylic acid) (PAA), polyethylenimine (PEI) and silica (SiO₂), as well as the immobilization of the magnetite-based catalysts in a mesoporous silica matrix, SBA-15. In the case of photo-Fenton catalysts, combinations of magnetite NPs with semiconductors were evaluated, so that magnetic recovery of the nanomaterials is possible, thus allowing a safe discharge free of NPs. The results of this study suggest that magnetic nanoparticles coated with PEI or PAA were the most suitable option for their applications in heterogeneous Fenton processes, while ZnO-Fe₃O₄ NPs provided an interesting approach in photo-Fenton. This work showed the importance of identifying the relevance of nanoparticle production strategy in the environmental impacts associated with their use. Full article