Collaborative adsorption and photocatalytic degradation of high concentration pharmaceutical pollutants in water using a novel dendritic fibrous nano-silica modified with chitosan and UiO-66.

This study presents a novel hybrid mesoporous material for degrading drug pollutants in water. The hybrid materials, derived from UiO-66 metal-organic framework and chitosan, coated on nano-silica, showed excellent drug adsorption through hydrogen-bonding interactions and efficient photodegradation of antibiotics. The hybrid material's enhanced conductivity and reduced band gap significantly improved pollution reduction by minimising electron-hole recombination. This allows for more efficient charge transport and better light absorption, boosting the material's ability to break down pollutants. Structural and morphological analyses were conducted using various techniques, including scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, Brunauer-Emmett-Teller analysis, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Optimising the adsorption-photodegradation process involved investigating pH, catalyst dose, and radiation time. Non-linear optimisation revealed an efficiency exceeding 85 % for 400 mg/L tetracycline and doxycycline, the model antibiotics. The optimal parameters for maximal elimination were determined as pH = 4.3, hybrid mesosphere dose = 4.0 mg/mL, and radiation time = 10 min. Kinetic studies favored pseudo-second-order diffusion models over pseudo-first-order models. The hybrid mesosphere showed sustained efficiency after three cycles and performed well in real aqueous samples, removing over 80 % of each antibiotic. This study demonstrates the potential of the hybrid mesoporous material for removing pharmaceutical pollutants in water systems.

Correction: A novel, efficient and magnetically recyclable Cu-Ni bimetallic nanocomposite as a highly active bifunctional catalyst for Pd-free Sonogashira and C-N cross-coupling reactions: a combined theoretical and experimental study.

[This corrects the article DOI: 10.1039/D3RA01965A.].

A novel, efficient and magnetically recyclable Cu-Ni bimetallic alloy nanoparticle as a highly active bifunctional catalyst for Pd-free Sonogashira and C-N cross-coupling reactions: a combined theoretical and experimental study.

In this study, a Fe3O4@SiO2@Cyt-Ni/Cu nanocomposite as a novel heterogeneous bimetallic catalyst was synthesized which exhibits efficient performance for the Sonogashira and C-N cross-coupling reactions. The characterization of the catalyst was studied by FT-IR, PXRD, VSM, EDX, TEM, FE-SEM and TGA analyses. The geometry optimization and relative energies of the designed bimetallic complexes were theoretically determined using density functional theory (DFT) calculation at the B3LYP/6-31G**/LANL2DZ level. The catalyst showed good activity in the coupling of various aryl halides with alkynes (Sonogashira reaction) as well as aryl halide with N-heterocycles and achieved coupling products with good to high yields for all of them in a short time. The high catalytic performance could be due to the synergistic effect between Ni and Cu, which causes the reaction to proceed more efficiently. This heterogeneous nanocatalyst could be easily recovered from the reaction mixture with an external magnet and reused for 7 consecutive runs with minimal loss of catalytic activity.

Copper adorned magnetic nanoparticles as a heterogeneous catalyst for Sonogashira coupling reaction in aqueous media.

A nanomagnetic hydrophilic heterogeneous copper catalyst, termed γ-Fe2O3@PEG@PAMAM G0-Cu, has been successfully prepared and characterized using FT-IR, XRD, FE-SEM, TEM, EDX, mapping, TGA/DTG, VSM and ICP analyses. The catalyst displayed excellent activity for the palladium-free Sonogashira cross coupling reaction of various aryl iodides and bromides with phenylacetylene derivatives in pure water. The presence of polyethylene glycol coupled with hydrophilic character of the Cu-catalyst adorned on γ-Fe2O3 MNPs provides the ready dispersion of the catalyst particles in water, leading to higher catalytic performance as well as facile catalyst recovery via simple magnetic decantation. The recovered catalyst was reused for at least six successive runs with little reduction in its catalytic activity and any noticeable changes in its structure. The use of water as a green solvent, without requiring any additive or organic solvent, as well as the exploitation of abundant and low-cost copper catalyst instead of expensive Pd catalyst along with the catalyst recovery and scalability, make this method favorable from environmental and economic points of view for the Sonogashira coupling reaction.

Dendritic structured palladium complexes: magnetically retrievable, highly efficient heterogeneous nanocatalyst for Suzuki and Heck cross-coupling reactions.

The recyclable nanomagnetic Pd-complex PAMAM G0-Pd@γ-Fe2O3 is reported for catalytic C-C cross-coupling reactions of challenging substrates. Mainly, a great variety of aryl chlorides can be used as substrates for Suzuki-Miyaura and Mizoroki-Heck reactions under mild reaction conditions (60-90 °C) and low catalyst loading (<1 mol% Pd) in aqueous media. The presence of numerous polar groups in the polymer matrix increases the solubility of the catalyst in water, thus facilitating its operation in aqueous environments. The immobilization of the catalyst on the surface of a magnetic platform allows its effective recovery and reuse without significant loss of catalytic activity for at least six cycles with total leaching of <1% palladium metal, meeting the requirements for acceptable metal residues in the pharmaceutical industry.

A Co-Cu bimetallic magnetic nanocatalyst with synergistic and bifunctional performance for the base-free Suzuki, Sonogashira, and C-N cross-coupling reactions in water.

A novel magnetically recyclable bimetallic catalyst was prepared by anchoring imidazolium moiety and PEG chains on Fe3O4 NPs and named as Fe3O4@PEG/Cu-Co. It was found to be a powerful catalyst for the Sonogashira, Suzuki, and C-N cross-coupling reactions in water as a green solvent without the need for any external base. Fe3O4@PEG/Cu-Co was well characterized with FT-IR, FE-SEM, TEM, VSM, EDX, ICP, UV-visible, CV, and XPS analyses. Optimum ranges of parameters such as time, temperature, and amount of catalyst were investigated by Design-Expert 10.0.7 software for C-C Suzuki, Sonogashira, and C-N cross-coupling reactions to find the optimum conditions. The catalyst was compatible with a variety of aryl halides and N-arenes and gave favorable coupling products with good to high yields for all of them. Hot filtration and Hg poisoning tests involving the nanocatalyst revealed the stability, low metal leaching, and heterogeneous nature of the catalyst. Reaction mechanisms were proposed by study of the UV-visible spectra in situ as well as hydroquinone tests during the progress of reactions. In situ XPS analysis was also used to study the reaction mechanism. To prove the synergistic performance of Co and Cu in the catalyst, its various homologues were synthesized and applied to a model reaction separately, and then their catalytic activities were investigated. Finally, the catalyst could be recovered from the reaction mixture simply, and reused for several cycles with a minimum loss in catalytic activity and performance.

Functionalized magnetic PAMAM dendrimer as an efficient nanocatalyst for a new synthetic strategy of xanthene pigments.

A green protocol has been developed for preparation of the wide variety of colored xanthene derivatives using a new efficient magnetic solid acid catalyst bearing polyamidoamine dendrimer moiety as a nanoscopic compound. Dendrimers, highly symmetric molecules around a core and 3D spherical morphology, show interesting traits based on their functionalized groups on the branched surface. They can be designed to provide water soluble structures or pseudo-active sites of biomolecules. The catalyst was assembled via a polyamidoamine dendrimer immobilized on the surface of γ-Fe2O3 followed by the sulfonylation of the amine groups by chlorosulfonic acid resulting in γ-Fe2O3@PAMAM-SO3H. Herein, PAMAM dendrimer with repeating amine/amide branches as catchable sites of sulfonic acid groups was introduced as transformer of homogeneous to heterogeneous acidic catalysts. The physicochemical properties of synthesized catalyst were studied using by FT-IR, FE-SEM, XRD, VSM, EDS, TGA/DTG, and TEM. Finally, the catalytic activity of γ-Fe2O3@PAMAM-SO3H was evaluated for the preparation of xanthene derivatives via a one-pot, three components reaction of aromatic aldehydes with i) ß-naphthol, ii) cyclic 1,3-dicarbonyl, iii) ß-naphthol and cyclic 1,3-dicarbonyl compounds, iv) 2-hydroxy-1,4-naphthoquinone, leading to the eco-riendly preparation of the target compounds in good to excellent yields. The catalyst could be easily recycled for at least five consecutive runs without significant loss in its catalytic activity.

Selective oxidation of alcohols and sulfides via O2 using a Co(ii) salen complex catalyst immobilized on KCC-1: synthesis and kinetic study.

The aim of this study was to immobilize a Co(ii) salen complex on KCC-1 as a catalyst that can be recovered (Co(ii) salen complex@KCC-1). Field-emission transmission electron microscopy, FT-IR spectroscopy, thermogravimetric analysis, elemental analysis, atomic absorption spectroscopy, and XRD were used to confirm the structure and chemical nature of Co(ii) salen complex@KCC-1. The oxidation efficiency was obtained for an extensive range of sulfides and alcohols using this sustainable catalyst, alongside O2 as an oxygen source and isobutyraldehyde (IBA) as an oxygen acceptor, with superior selectivity and conversion for the relevant oxidation products (sulfoxides and ketones or aldehydes) under moderate conditions. The µ-oxo and peroxo groups on the ligands of the Co complex appeared to be responsible for the superior activity of the catalyst. Essential factors behind the oxidation of alcohol and sulfoxides were investigated, including the catalyst, solvent, and temperature. In this paper, molecular oxygen (O2) was used as a green oxidant. Furthermore, kinetic studies were conducted, revealing a first-order reaction for the oxidation of both benzyl alcohol and sulfide. The reaction progressed at mild temperature, and the catalyst could be easily recovered and reused for numerous consecutive runs under the reaction conditions, without any substantial reduction in the functionality of the catalytic system.

The CuFe2O4@SiO2@ZrO2/SO4 2-/Cu nanoparticles: an efficient magnetically recyclable multifunctional Lewis/Brønsted acid nanocatalyst for the ligand- and Pd-free Sonogashira cross-coupling reaction in water.

Herein, the synthesis and application of copper-incorporated sulfated zirconium oxide supported on CuFe2O4 NPs (CuFe2O4@SiO2@ZrO2/SO4 2-/Cu NPs) as a novel Lewis/Brønsted acid nanocatalyst were studied for the Sonogashira C-C cross-coupling reaction. The fabricated CuFe2O4@SiO2@ZrO2/SO4 2-/Cu catalyst exhibited efficient activity for a large variety of aryl iodides/bromides and, most importantly, aryl chlorides in water and in the presence of NaOH as a base in short reaction times. The catalyst was fully characterized by FTIR, TG-DTG, VSM, XRD, EDX, FE-SEM and TEM analyses. A synergetic effect could be considered to have arisen from the various Lewis acid and Brønsted acid sites present in the catalyst. The efficient incorporation of copper into zirconia provided a robust highly stable hybrid, which prevented any metal leaching, whether from the magnetite moiety and/or Cu sites in the reaction mixture. Moreover, the catalyst was successfully recovered from the mixture by a simple external magnet and reused for at least 9 consecutive runs. Zero metal leaching, stability, consistency with a variety of substrates, fast performance, cost-effectiveness, environmental friendliness, and preparation with accessible and cheap materials are some of the advantages and highlights of the current protocol.

Synthesis and characterizations of a novel CoFe2O4@CuS magnetic nanocomposite and investigation of its efficiency for photocatalytic degradation of penicillin G antibiotic in simulated wastewater.

In the present study, efficiency of a new magnetic nanocomposite (CoFe2O4@CuS) for photocatalytic degradation of PG in aqueous solutions was investigated. Structural characteristics of synthesized magnetic nanoparticles were determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), vibrating-sample magnetometer (VSM), Thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET), Energy-dispersive X-ray spectroscopy (EDX) and Raman spectroscopy. Also, the effect of important parameters such as pH (3-11), nanoparticle dosage (0.1-0.8 g/L), PG concentration (10-100 mg/L) and contact time (10-120 min) were investigated. Results of FT-IR, XRD, EDX and Raman analyses showed successful synthesis of CoFe2O4@CuS magnetic nanocomposite. SEM and TEM images showed that the size of CoFe2O4@CuS magnetic nanocomposite was below 100 nm. Also, results of VSM analyses showed that CoFe2O4@CuS magnetic nanocomposite still has magnetic properties (Ms = 7.76 emu/g). According to the results of study, in photocatalytic degradation process of PG by CoFe2O4@CuS magnetic nanocomposite by UV light and in optimum condition (pH = 5, nanocomposite dose: 0.2 g/L, PG concentration: 10 mg/L and contact time: 120 min), maximum degradation of PG was 70.7%. Also the photocatalytic reaction almost followed the pseudo-first order kinetics. In addition, after five consecutive runs, the catalyst efficiency wasn't reduced significantly.

Modified nickel ferrite nanocomposite/functionalized chitosan as a novel adsorbent for the removal of acidic dyes.

As a new type of magnetic adsorbent, a nickel ferrite nanocomposite modified by functionalized chitosan was developed to remove methyl orange and Congo red from aqueous solutions. This new adsorbent was characterized and utilizing batch adsorption approach, the mechanism of methyl orange and Congo red removal were probed. Following that the study on pertinent parameters which could influence the efficiency of the dyes removal, i.e. pH of the solution, initial dye concentration, dose of the adsorbent, and contact time were accomplished in order to arrive their optimized values by using response surface methodology. In addition, kinetics and isotherm studies were conducted on the developed system. Langmuir model was used to probe adsorption isotherm, acquiring adsorption capacity of 551.2 and 274.7 mg g-1 for methyl orange and Congo red, respectively. Both of methyl orange and Congo red adsorption kinetics obeyed a pseudo-second-order kinetic model, indicating that adsorption was the rate-limiting step and only 5 min was required to remove 50% of dyes. The fitting of experimental data was fulfilled with intra-particle diffusion reaching to conclusion that the adsorption kinetic could be controlled simultaneously by film diffusion and intra-particle diffusion. Furthermore, the desorption studies of dyes showed that the adsorbent is reusable.