Iranian Journal of Catalysis
Volume:14 Issue: 2, Spring 2024

Continued research on pyrazoline derivatives with excellent biological activities has encouraged us to design and synthesize 1,3,5-trisubstituted pyrazoline series introducing NiFe2O4.Cu(OH)2 magnetic nanocomposite as a heterogeneous catalyst by the combination of highly substituted aryl aldehydes, substituted acetophenones, and acetyl hydrazine hydrate under ultrasound irradiation at 50oC. The NiFe2O4.Cu(OH)2 magnetic nanocomposite materials are characterized by X-ray diffraction and Transmission electron microscopy. The characterized title compounds were studied for theoretical DFT studies using Spartan-14 software and molecular docking studies with Autodock Vina and Discovery Studio software to examine their antifungal activity efficiency against CaCYP51 (PDB ID-5EQB). Highlights ·  NiFe2O4.Cu(OH)2 nanocomposite was synthesized and characterized.·The synthesized nanocomposite was used as a powerful heterogeneous catalyst.·Synthesis of 1,3,5-trisubstituted pyrazoline derivatives was done using NiFe2O4.Cu(OH)2 catalyst under the irradiation of ultrasound·Recyclability of NiFe2O4.Cu(OH)2 catalyst was investigated.·The synthesized nanocomposite was studied for theoretical DFT studies.

This article investigates an efficient and eco-friendly protocol for protecting amines and alcohols as important molecules in organic chemistry, using Fe3O4@MCM-41/Zr@Piperazine as a newly reported magnetic mesoporous nanostructured catalyst. Firstly, the protection of alcohols was developed through their transformation to trimethylsilyl ethers. Then this reagent was applied for the acceleration of the acetylation of amines and alcohols with acetic anhydride and acetyl chloride, respectively. Finally, the influence of this highly active nanocatalyst on the formyl protection of amines was studied. The outgoings of these works illustrated the superiorities of this functionalized mesoporous mixed metal nanocatalyst in terms of accomplishing the reactions in high yields during proper reaction times and its superparamagnetic nature leading to easy separation, and several times, reusability. Highlights  1. Investigating the catalytic effect of Fe3O4@MCM-41@NH-SO3H,on some protection reactions of amino and alcoholic groups.2.  Use of a newly reported magnetic mesoporous silica nanostructured catalyst in organic reactions.3. The successful synthesis of formamides, trimethylsilyl ethers, acetamides and acetate derivatives via a green, easy and simple experimental procedure.4. Accomplishing the reactions in high yields during proper reaction times.5. Easy separation and reusability of the catalyst due to its superparamagnetic nature.

In this study, the preparation of a new functionalized acidic metal-organic framework nanocatalyst formulated as Zr-MOF-N=CH-C6H4-SO3H has been reported. After characterization using different analysis methods such as FT-IR, XRD, SEM, EDX, TGA, and TEM, the average size of the nanoparticles was found to be between 42.5 and 50.4 nm in diameter. The Nanocatalyst was utilized in the synthesis of novel substituted 4-aminocoumarin analogs via one-pot three-component reaction of 4-aminocoumarin, arylaldehyde or 3-(2-aryldiazenyl)-2-hydroxybenzaldehyde, and 6-hydroxyuracil or 1,3-dimethylbarbituric acid in good-to-excellent yields in ethanol at reflux conditions. A λmax of 362.7 nm was observed for compound 4e. Simple work-up of the process, mild reaction conditions, no by-products and easy reusability of the nanocatalyst are some of the advantages of the procedure. Highlights  ·A novel series of substituted 4-aminocoumarin analogs were synthesized.A new functionalized acidic metal-organic framework catalyst Zr-MOF-N=CH-C6H4-OSO3H was introduced.· High yields and easy work-up procedure are some advantages of this method.·A λmax of 362.7 nm was observed for compound 4e.The catalyst is easily recycled.

A facile chemical mixing approach was used to prepare TiO2/ZnO photocatalystswith different mass ratios. The photodegradation activity was tested against paracetamol in an aqueous phase assisted by low UVC-light intensity (9 W). TiO2/ZnO particles mainly exhibited irregular shapes with uniform distributions and high crystallinity degree, the primary oxidation state in the structure is titanium Ti4+ of anatase TiO2 (459.2 and 464.9 eV), and the presence of standard chemical state of Zn2+ (1021.9 and 1044.9 eV). The composite with a 1:5 mass ratio displayed a rapid and outstanding degradation percentage of 95% and a rate of 1.83 × 10-2 min-1. The best photocatalyst can be recycled up to five times towards paracetamol degradation without any regeneration step or severe deactivation. A Fuzzy inference system (FIS) was computed for the first time to investigate the relationship between the TiO2/ZnO ratio, degradation percentage, and rate constant. The optimal concentration of 9 mg/L was obtained, whereby the degradation percentage and rate were sufficiently maintained above 90% and 0.19 mg/L.min, respectively. Using a fuzzy logic controller (FLC) in this work enables future guidance and prediction for developing the best TiO2/ZnO photocatalysts for real-world water remediation processes.Highlights 1.      Facile preparation of TiO2/ZnO composite photocatalyst via simple mixing for degradation of paracetamol under low UVC light intensity (9 W).  2.      TiO2/ZnO particles are mostly exhibited irregular shapes with uniform distributions and high crystallinity degree, the main oxidation state in the structure is titanium Ti4+ of anatase TiO2 (459.2 and 464.9 eV), and the presence of standard chemical state of Zn2+ (1021.9 and 1044.9 eV).  3.      TiO2/ZnO (1:5) displayed a rapid and outstanding degradation percentage of 95% and rate of 1.83 × 10-2 min-1, in accordance with pseudo first-order kinetics. 4.      The optimal concentration of 9 mg/L was computed by the prediction using fuzzy inference system (FIS) for the first time, whereby the degradation percentage and rate were sufficiently maintained above 90% and 0.19 mg/L.min, respectively. 5.      The stability of TiO2/ZnO composite photocatalyst towards paracetamol degradation was retained up to 5 cycles, without undergo any regeneration procedure.

TiO2 is a highly desirable photocatalyst due to its abundance and low cost. However, its large band gap restricts its ability to absorb a significant portion of visible light. This issue can be addressed through cationic or anionic doping. In these instances, the impurity bands reduce the band gap. Nevertheless, in order to enhance the photocatalytic activity, these bands need to be distributed among the atoms. In this study, we investigated the electronic structures of rutile bulk phases co-doped with cobalt and nitrogen. Data show that the single doping of rutile by N and Co reduces the band gap by 26% and 42%, respectively. For the (N, Co) dual-doped rutile, the band gap value depends on the relative position of the dopants. When placed in the nearest neighbor configuration (nearest model), the band gap only decreases by 25%. However, if the dopants are positioned far from each other (far model), the catalyst becomes half-metallic with the spin-down channel’s band gap equal to zero. The calculated spatial delocalization indices (SDI) for the impurity bands reveal that the far model of (N, Co) dual-doped TiO2 exhibits the highest SDI value compared to the other cases. All studied catalysts displayed magnetic properties. The magnetic moments of single-doped catalysts are 1 μB, while the magnetic moment of the dual-doped catalyst is 2μB.  Highlights  Hybrid method of PBE0 was used to calculate optical band gaps of pure and doped rutile. All the doped TiO2 are visible active photocatalysts. In some cases, the band gap is less than 2.0 eV, which are good candidates for solar photocatalysts. All predicted data are in line with the available experimental ones. Hybrid data show that the (N, Co) dual doped TiO2 is a half-metal and could be used in spintronics.

The sonocatalytic activity of the particles of the green Maghnite-H+ sonocatalyst was tested by the degradation of 2-Mercaptobenzothiazole (MBT) under ultrasonic irradiation was performed in an ultrasonic bath with a frequency of 40 kHz, and an ultrasonic power of 120 W for 120 min at room temperature followed by UV-visible analysis. This study was accompanied by the application of a commercial catalyst approved in the literature, TiO2-anatase. The catalysts used were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Brunauer–Emmett–Teller (BET), and the band gap energy of Maghnite-H+ was determined by the Tauc method. Different experimental conditions, such as the dose of the catalyst, the initial concentration of MBT, and the addition of H2O2, were studied to determine their effects on sonocatalytic degradation. At a concentration of [MBT] = 10 mg. L-1, the degradation rates of MBT after 120 min of sonocatalysis are 94.29% for Maghnite-H+ and 40.22% for TiO2-anatase. The effect of the concentration of MBT is proportional to the rate of degradation. The addition of H2O2 (0.5 mol. L-1) improved the efficiency of the degradation to 97% for the Maghnite-H+ and 87.85% for the TiO2-anatase. For an initial MBT concentration of 10 mg. L-1, the total organic carbon (TOC) measurement revealed that after 120 minutes, 82.79% and 28.54% mineralization was observed for US/Maghnite-H+ and US/TiO2 systems, respectively.  Highlights§  Preparation of Maghnite-H+,§  The Maghnite-H+ and TiO2 used were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and the band gap energy of Maghnite-H+ was determined by the Tauc method.§  Study of the sonocatalytic activity of the green Maghnite-H+ sonocatalyst was tested by the degradation of 2-Mercaptobenzothiazole (MBT) under ultrasonic irradiation was performed in an ultrasonic bath  (frequency of 40 kHz, and an ultrasonic power of 120 W) for 120 min at room temperature. §  This study was accompanied by applying a commercial catalyst approved in the literature, TiO2-anatase.§  Different experimental conditions such as catalyst dose, initial MBT concentration, and H2O2 addition were investigated to determine their effects on the sonocatalytic degradation of MBT. §  Study of UV-visible absorption spectra and reaction mechanism.

Functionalized 2-amino-4H-chromenes have been successfully synthesized via cyclization of C-H activated acids, aromatic aldehydes, and active methylene compounds using a natural base catalyst derived from waste snail shells (Bellamya bengalensis) in the water at ambient temperature. Freshwater snail shells are significant biological materials with diverse uses. As an economical and environmentally benign alternative to traditional stoichiometric reagents and expensive metal catalysts, the waste shells of snails worked well as a heterogeneous base catalyst in hetero-cyclization. The as-prepared catalyst was analyzed using FTIR, XRD, EDS, SEM, TEM, and TGA tools. The chemical analysis revealed the predominance of CaO, which in the water possibly provides an alkaline medium to the reaction through which the reaction accelerates efficiently and offers a quantitative yield of the desired product. Catalytic reusability showed slight leaching of the catalyst that could be recovered and reused.  Highlights ·Waste shells of snail-derived catalyst employed in synthesizing densely functionalized 2-amino-4H-chromenes. ·Utilization of natural feedstock in catalysis leads to cost-efficient and sustainable methodology.·Characterization tools exhibited a higher concentration of Ca species in snail shells.CaO-enriched catalyst possibly responsible for promoting heterocyclization more efficiently in an aqueous medium.·  Green credentials of the protocol are enhanced using water as a solvent, ambient temperature conditions, and achieving high yields.

In this study, N1-N4-bis (3-(trimethoxysilyl)propyl)butane-1,4-diammonium trinitromethanide on titanium dioxide {TiO2-Bis[TMS-NH2+ C(NO2)3-]}an , was prepared and characterized by the use of different techniques including energy dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FT-IR), thermo gravimetric analysis (TGA), field emission scanning electron microscopy (FESEM), and X-ray diffraction (XRD). In continue, the use of the prepared reagent as an efficient nano-catalyst was examined in the acetylation of amines and alcohols under mild reaction conditions with good to excellent yields. In the studied reactions the catalyst can be recycled and reused for an acceptable period of runs. Highlights v  Introduction of TiO2-Bis [TMS-NH2+ C(NO2)3-] as an effective and new nanocatalyst for the acetylation of amines and alcohols.v  Identification of the catalyst structure using (FT-IR), (EDX), (FESEM), (TGA), and (XRD).vThe attractive features of this process are: short reaction times, easy work-up produce, performing the reaction in the absence of solvent, and easy separation from the reaction mixture.v  Reusability of the catalyst.

Ag, Ce co-doped ZnO-polyaniline (Ag-Ce/ZnO-PANI) and Ag, Ce co-doped ZnO-reduced graphene oxide (Ag-Ce/ZnO-rGO) were synthesized via precipitation and in-situ polymerization, an environmentally friendly process. Structural and optical properties were characterized using X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), transmission electron microscopy (TEM), diffuse reflectance spectra (DRS), N2 adsorption-desorption, photoluminescence spectra (PL), and Energy Dispersive X-ray analysis (EDX). The nanocomposites exhibited crystalline structures, with ZnO, metallic silver, and cubic crystalline CeO2 identified in Ag-Ce-ZnO samples. Morphological studies revealed spherical shapes for ZnO and Ag-Ce-ZnO, while PANI displayed a fibrous structure. EDX confirmed elemental composition without impurities, and compositional mapping showed uniform dispersion. The photocatalytic degradation of Malachite green and para nitrophenol was performed using the nanocomposites under visible light irradiation. Among them, Ag-Ce/ZnO-rGO demonstrated significant photocatalytic efficiency, achieving 92% and 98% degradation of the organic contaminants, respectively. This enhanced activity can be attributed to increased specific surface area, efficient separation of photoinduced electron-hole pairs, enhanced dye adsorption, strong visible light absorption, and rapid transfer processes. Moreover, Ag-Ce/ZnO-rGO exhibited efficient reusability for five degradation cycles. Highlights ·Surface area plays an imperative role in characterizing the capability of a catalyst, it represents the catalyst’s ability to absorb contaminants.· co-doping of the Ag and Ce to the nanocomposites improved the results obtained from the refined degradation.·The presence of rGO in the synthesized nanocomposite will improve the electron transfer between the catalyst and the pollutants.· Silver and cerium presence contributes to delaying the electron-hole recombination process.· The utilization of synthesized nanocomposites for the degradation of Malachite green and para nitrophenol under visible light irradiation.

A novel ligand, (E)-5-((2-hydroxy-4,6-dimethylphenyl)diazenyl)-2,3-dihydrophthalazine-1,4-dione, was synthesized through the reaction of 3,5-dimethylphenol with the diazonium salt of 5-amino-2,3-dihydrophthalazine-1,4-dione. The ligand underwent characterization through the utilization of diverse spectroscopic methods, including UV-Vis, FT-IR, 13C and 1H-NMR, alongside Mass spectroscopy and microelemental analysis (Carbon, Hydrogen, Nitrogen, Oxygen). Metal chelates of transition metals were prepared and analyzed using elemental analysis, mass spectra, atomic absorption, UV-Vis, FT-IR spectral analysis, as well as conductivity and magnetic measurements. The investigation into the compounds' nature was conducted by utilizing mole ratio and continuous contrast methods, where Beer's law was adhered to over a concentration range of 1×10-4-3×10-4 mol/L. The determination of the molar absorptivity of the compound solutions was carried out. Analytical data analysis indicated that all complexes demonstrated a metal-ligand ratio of 1:2, with the exception of the palladium complex, which exhibited a 1:1 ratio. Physicochemical data indicated an octahedral structure for Pt (IV) and Ni (II) complexes, and a square planar structure for the Pd (II) complex. The Pd complex was utilized in a carbon-carbon Suzuki coupling reaction to evaluate the application of this complex. Furthermore, the biological activity of these complexes was assessed on the proliferation of human blood lymphocytes. The results demonstrated that the ligand inhibited cell division at varying levels, with the inhibition increasing with higher concentrations. Furthermore, the Pd complex caused a prolonged arrest during mitosis at the boundary between metaphase and anaphase, leading to the suppression of proliferation in the lymphocyte cell line. The stability of the dyes was assessed in terms of light exposure and resistance to detergents. Highlights  · A novel azo ligand was synthesized from the reaction of 3,5-dimethylphenol and diazonium salts.·The prepared ligands were metalated with Ni (II), Pd (II), and Pt (IV).· The synthesized metal complexes were characterized using UV-Vis, FT-IR and etc.·The Pd (II) complex was used in Suzuki cross coupling reaction.

In this research, we reported Fe3O4@SiO2@NCs@Al2O3 [FSNCA] nanoparticles as an efficient catalyst for the synthesis of Tetrahydrobenzopyrans (THBPS) in water solvent at room temperature with short reaction time. The catalyst exhibits excellent catalytic activity, selectivity, and recyclability. The nanocatalyst structure was characterized by FT-IR, SEM, XRD, TGA, VSM, and EDS. There are significant advantages of using the FSNCA nanocatalyst such as the primary benefit is the increase in production efficiency. By enabling a one-pot synthesis process, this nanocatalyst decreases the stages required for reaction, reducing time and energy consumption. Furthermore, the possibility of recycling the catalyst contributes to economic efficiency, minimizing waste production, thereby aligning with the principles of green chemistry.Highlights 1.This research describes the catalytic activity of a nanocatalyst made of the materials available which are easily and quite prevalent in nature.2.The nanoparticles efficiently catalyze the synthesis of Tetrahydrobenzo[b]pyran derivatives and this method is superior in terms of the reaction temperature, green solvent and yields.3.No side reactions, Product’s purity and yield enhanced by Fe3O4@SiO2@NCs@Al2O3 as green magnetic catalyst.4.Clean separation and recyclability of the catalyst 5.The article meet the principles of Green chemistry

This paper uses a one-step synthesis method to prepare NH2-ZIF-8/NCDs porous materials. A series of composite photocatalysts were obtained by adjusting the additional amount of nitrogen-doped carbon quantum dots (NCDs). The structural characteristics of the nanocomposites were characterized using XRD, FTIR, FESEM, TEM, and BET. The photocatalytic activity of NH2-ZIF-8/NCDs nanocomposites was investigated through the photocatalytic degradation of methylene blue (MB). The results show that when the addition amount of ethylenediamine and NCDs is 1:5, the prepared NH2-ZIF-8/NCDs catalyst can degrade 76.2% of the 20 mg/L methylene blue (MB) solution within 5 minutes of illumination. 97.1% of MB was degraded after 60 minutes. The photocatalytic activity of NH2-ZIF-8/NCDs photocatalyst is higher than that of ZIF-8 and ZIF-8/NCDs photocatalyst. Free radical capture experiments showed that hydroxyl radicals (·OH) were the main active species responsible for removing MB under light illumination.  Highlights  ü NH2-ZIF-8/NCDs prepared by the one-step synthesis method.ü Adding ethylenediamine for amine modification changed the structure of ZIF-8 to a porous structure and increased the reaction sites of the catalyst.ü Adding NCDs can achieve good charge separation efficiency.ü NH2-ZIF-8/NCDs catalyst exhibits excellent photocatalytic performance.