Preparation of magnetic biochar functionalized by polyvinyl imidazole and palladium nanoparticles for the catalysis of nitroarenes hydrogenation and Sonogashira reaction.

Catalysts are essential materials in biotechnology, medicine, industry, and chemistry. On the other hand, recycling and using waste materials is important in economic efficiency and green chemistry. Thus, biochar was prepared from the stem and roots of the Spear Thistle to recover waste. After magnetizing the biochar, its surface was modified with polyvinyl imidazole. Finally, this modified biochar was decorated with Pd nanoparticles and used as a selective and recyclable nanocatalyst in the hydrogenation of nitroarenes and the Sonogashira reaction. The structure of this organic-inorganic nanocatalyst has been characterized by FESEM-EDS, XRD, FT-IR, TEM, and VSM techniques. In the hydrogenation reaction with the amount of 30 mg of nanocatalyst, the temperature of 50 °C in the water solvent, the reaction efficiency reached 99% for 30 min. In addition, under optimal conditions for the Sonogashira reaction: 1.0 mmol iodobenzene, 1.2 mmol phenylacetylene, 20 mg MBC-PVIm/Pd, 2 mmol K2CO3 in H2O at 50 C for 15 min, the reaction efficiency reached 95%. The recyclability of magnetic nanocatalysts was investigated and recognized this nanocatalyst can be used several times without notable loss of its activity.

Recent advances in the application of magnetic nanocatalysts in multicomponent reactions.

Recently, the preparation and applications of magnetic nanostructures have attracted increasing attention in nanocatalysis studies, and magnetic nanoparticle (MNP) functionalized catalysts have been applied in important reactions such as Suzuki-Miyaura and Heck couplings. The modified nanocomposites demonstrate significant catalytic efficiency and excellent benefits in the context of catalyst recovery methods. This review discusses the recent modified magnetic nanocomposites in the field of catalytic applications along with the synthetic processes that are usually employed.

Magnetic bentonite decorated with Pd nanoparticles and cross-linked polyvinyl pyridine as an efficient nanocatalyst for Suzuki coupling and 4-Nitrophenol reduction reactions.

This study reports the preparation of a novel type of support based on magnetically recyclable bentonite functionalized with divinylbenzene-polyvinyl pyridine (PVP-DVB) for Pd (II) nanocatalyst by a simple cost-effective method. Firstly, the conventional co-precipitation method synthesized Fe3O4 nanoparticles (NPs) onto bentonite sheets. Then the prepared magnetic support surface was functionalized by divinylbenzene-polyvinyl pyridine (PVP-DVB) to create a cross-linked polymer with a high coordination ability with palladium. Repeated nitrogen units in the PVP-DVB polymer chain increase the number of Pd bonds and thus lead to higher performance of the nanocatalyst. Finally, the palladium NPs were simultaneously synthesized and immobilized under mild conditions. The synthesized nanocatalyst was characterized by several methods such as scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, vibrating sample magnetometer, inductively coupled plasma mass spectrometry and thermogravimetric analysis. The efficiency of synthesized heterogeneous nanocatalyst was investigated in Suzuki-Miyaura cross-coupling reactions between a range of aryl halides (X = Cl, Br, I) with phenylboronic acid and in the reduction of 4-nitrophenol (4-NP). Moreover, the synthesized nanocatalyst could be easily recovered and reused several times with an efficiency greater than 90%.

The preparation of polyvinyl imidazole-functionalized magnetic biochar decorated by silver nanoparticles as an efficient catalyst for the synthesis of spiro-2-Amino-4H-pyran compounds.

The silver nanoparticle was synthesized by developing poly (1-vinylimidazole) on the surface of magnetized biochar (the stem and roots of Spear Thistle) (biochar/Fe3O4/PVIm/Ag). This nanocomposite was characterized by Fourier-transformed infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), vibrating sample magnetometer (VSM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), and transmission electron microscopy (TEM). The SEM and TEM images of the nanocatalyst, biochar/Fe3O4/PVIm/Ag-NPs, confirmed the observation of microscopic sheets of biochar. The catalytic activity of these Ag NPs was tested via multicomponent reaction plus reusing to successful formation of 2-amino-4H-pyran and functionalized spirochromen derivatives. The prepared nanocatalyst was easily separated by an external magnet and reused in repeating coupling reaction cycles four times without remarkable activity loss. The catalyst showed great efficiency and reusability, thus making it an ideal candidate for catalytic purposes in several organic transformations.

An intelligent DNA nanorobot for detection of MiRNAs cancer biomarkers using molecular programming to fabricate a logic-responsive hybrid nanostructure.

Herein, we designed a DNA framework-based intelligent nanorobot using toehold-mediated strand displacement reaction-based molecular programming and logic gate operation for the selective and synchronous detection of miR21 and miR125b, which are known as significant cancer biomarkers. Moreover, to investigate the applicability of our design, DNA nanorobots were implemented as capping agents onto the pores of MSNs. These agents can develop a logic-responsive hybrid nanostructure capable of specific drug release in the presence of both targets. The prosperous synthesis steps were verified by FTIR, XRD, BET, UV-visible, FESEM-EDX mapping, and HRTEM analyses. Finally, the proper release of the drug in the presence of both target microRNAs was studied. This Hybrid DNA Nanostructure was designed with the possibility to respond to any target oligonucleotides with 22 nucleotides length.

Synthesis of Ag nanoparticles by Celery leaves extract supported on magnetic biochar substrate, as a catalyst for the reduction reactions.

Green synthesis of a noble metal such as Ag nanoparticles is an enormously developed research area. In this study, a biochar/Fe3O4-Ag magnetic nanocatalyst was produced via a green path by using Celery stalk as a carbon-based substrate and Celery leaf extract as reducing and stabilizing agents to construct Ag nanoparticles. The synthesized nanocatalyst was determined using various techniques, such as UV-Vis spectroscopy, FT-IR spectroscopy, XRD (X-ray diffraction), SEM/EDX spectroscopy (scanning electron microscopy/energy-dispersive X-ray), TEM (transmission electron microscopy), and VSM (vibrating sample magnetometer). To survey the catalytic action of the biochar/Fe3O4-Ag nanocatalyst, it was used in the reduction reaction of disparate nitroaromatics, aldehydes, and ketones. This catalyst has demonstrated good characteristics in terms of the amount, reusability, recoverability, activity, and structural integrity of the catalyst during the reaction. In addition, biochar/Fe3O4-Ag could be detached magnetically and recycled multiple times without significantly reducing its catalytic performance.

Layered double hydroxides as heterogeneous catalyst systems in the cross-coupling reactions: an overview.

Layered double hydroxides (LDHs) are recognized as two-dimensional (2D) clay materials, which comprise the interlayer anions and host layers with a positive charge (brucite-like M(OH)6 octahedral). They have been used as effective and eco-friendly heterogeneous catalytic systems in cross-coupling reactions. In this review, we try to underscore the applications of (LDHs) as an efficient and green catalyst in some important name reactions, namely Suzuki, Heck, Sonogashira, and Ullmann cross-coupling reactions leading to carbon-carbon bond formations.

Ag nanoparticles immobilized on new magnetic alginate halloysite as a recoverable catalyst for reduction of nitroaromatics in aqueous media.

Amines can be applied in the synthesis of various important compounds such as dyes, drugs, polymers, pharmaceutical products, and biologically active materials. The significant subject in the preparation of amines is the selection of the most effective heterogeneous catalyst to get the best catalytic efficiency, stability, recoverability, and reusability. For this target, we prepared new alginate magnetically recoverable nanocatalyst by stabilization of Ag nanoparticles on the surface of the halloysite (HS) [HS-Alginate-Ag/Fe3O4]. Several detection methods confirmed the production of HS-Alginate-Ag/Fe3O4 nanocatalyst and the results obtained were well explained in the context. HS-Alginate-Ag/Fe3O4 presented good catalytic performance for the hydrogenation of nitro compounds using NaBH4 as the reducing agent and hydrogen donor. The good activity and durability of this catalyst can be attributed to the good dispersion and nano-sized particle of silver nanoparticles.

Silver incorporated into g-C3N4/Alginate as an efficient and heterogeneous catalyst for promoting click and A3 and KA2 coupling reaction.

Fe3O4/g-C3N4/Alginate-Ag nanocomposite as a novel and effective nanocatalyst was successfully prepared. This nanocomposite was fully characterized using several techniques such as X-ray diffraction (XRD), field emission scanning electron microscopy with energy dispersive spectroscopy (FESEM-EDS), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). In addition, the catalytic activity of this novel and characterized nanocatalyst was investigated in the regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles via click reaction and A3 and KA2 coupling reaction in aqueous media. The prepared nanocatalyst was simply recovered by using an external magnet and reused for several times with a slight loss of catalytic activity.

Gold nanoparticles decorated biguanidine modified mesoporous silica KIT-5 as recoverable heterogeneous catalyst for the reductive degradation of environmental contaminants.

This current study involves the novel synthesis of Au nanoparticles (Au NPs) decorated biguanidine modified mesoporous silica KIT-5 following post-functionalization approach. The tiny Au NPs were being stabilized over the in situ prepared biguanidine ligand. The high surface area material was characterized using analytical techniques like Fourier Transformed infrared (FT-IR) spectroscopy, N2-adsorption-desorption isotherm, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy Dispersive X-ray Spectroscopy (EDS), and X-ray Diffraction study (XRD). Our material was found to be an efficient catalyst in the reductive degradation of harmful water contaminating organic dyes like Methylene blue (MB), Methyl Orange (MO) and Rhodamin B (RhB) in presence of NaBH4 at room temperature. The whole procedure was followed up with the help of time dependant UV-Vis spectroscopy. All the reactions followed pseudo-unimolecular kinetics and corresponding rate constant were determined. The reduction rate becomes high in presence of higher load of catalysts.

Ag nanoparticles immobilized on new mesoporous triazine-based carbon (MTC) as green and recoverable catalyst for reduction of nitroaromatic in aqueous media.

In this research, we reported an effective method for the synthesis of a new mesoporous triazine-based carbon (MTC) substrate and its application as the green and recoverable catalyst in the synthesis of organic compounds. The porous carbon acted as a substrate for silver active species after its surface modification by chloroacetonitrile (Ag@MTC). The Ag@MTC nanocatalyst was characterized by several techniques namely, Fourier-transform infrared spectroscopy, field emission scanning electron microscopy with energy dispersive spectroscopy, X-ray diffraction, transmission electron microscopy, Brunauer-Emmett-Teller surface area analysis, and inductively coupled plasma. The Ag@MTC catalyst was applied for the reduction of nitroaromatic compounds in aqueous media by using NaBH4 (reducing agent) at room temperature. This nanocatalyst can be readily recovered and recycled for at least nine runs without a notable decrease in its efficiency. Catalytic efficiency studies exhibited that Ag@MTC nanocatalyst had good activity towards reduction reactions.

Bio-assisted synthesized Pd nanoparticles supported on ionic liquid decorated magnetic halloysite: an efficient catalyst for degradation of dyes.

Using natural materials, i.e. halloysite nanoclay that is a biocompatible naturally occurring clay and Heracleum persicum extract that can serve as a green reducing agent, a novel magnetic catalyst, Fe3O4/Hal-Mel-TEA(IL)-Pd, has been designed and fabricated. To prepare the catalyst, halloysite was first magnetized (magnetic particles with mean diameter of 13.06 ± 3.1 nm) and then surface functionalized with melamine, 1,4 dibromobutane and triethanolamine to provide ionic liquid on the halloysite surface (5 wt%). The latter was then used as a support to immobilize Pd nanoparticles that were reduced by Heracleum persicum extract. The characterization of the catalyst established that the loading of Pd in Fe3O4/Hal-Mel-TEA(IL)-Pd was very low (0.93 wt%) and its specific surface area was 63 m2g-1. Moreover, the catalyst showed magnetic property (Ms = 19.75 emu g-1) and could be magnetically separated from the reaction. The catalytic performance of the magnetic catalyst for reductive degradation of methyl orange and rhodamine B in the presence of NaBH4 in aqueous media was investigated. The activation energy, enthalpy, and entropy for the reduction of methyl orange were estimated as 42.02 kJ mol-1, 39.40 kJ mol-1, and -139.06 J mol-1 K-1, respectively. These values for rhodamine B were calculated as 39.97 kJ mol-1, 34.33 kJ mol-1, and -155.18 Jmol-1K-1, respectively. Notably, Fe3O4/Hal-Mel-TEA(IL)-Pd could be reused for eight reaction runs with negligible loss of the catalytic activity (~3%) and Pd leaching (0.01 wt% of the initial loading).

Green synthesis of Ag NPs on magnetic polyallylamine decorated g-C3N4 by Heracleum persicum extract: efficient catalyst for reduction of dyes.

Silver nanoparticles were immobilized on magnetic polyallylamine (PAA) decorated g-C3N4 by using Heracleum persicum extract as a biological reducing and stabilizing agent. The resulting nanocomposite, Fe3O4-g-C3N4-TCT-PAA-Ag, was then characterized using BET, VSM, XRD, TGA, FTIR, TEM, EDS and ICP. The catalytic performance of the synthesized nanocatalyst was considered in the reduction of rhodamine B, and methyl orange in the presence of sodium borohydride in the aqueous medium at room temperature. The results showed that Fe3O4-g-C3N4-TCT-PAA-Ag nanocomposite could promote both reduction reactions efficiently in very short reaction times (70-100 s). In addition, Fe3O4-g-C3N4-TCT-PAA-Ag could be magnetically recovered and recycled for several cycles with no significant decrease in its catalytic performance. Using the experimental results, the rate constant, enthalpy, and entropy of the reduction reactions of both dyes were estimated.

In Situ Immobilized Silver Nanoparticles on Rubia tinctorum Extract-Coated Ultrasmall Iron Oxide Nanoparticles: An Efficient Nanocatalyst with Magnetic Recyclability for Synthesis of Propargylamines by A3 Coupling Reaction.

This research suggests a green method for synthesizing hybrid magnetic nanocomposites that can be used as a reductant and a stabilizing agent for immobilizing metal nanoparticles (NPs). The central idea is the modification of magnetic NPs using Rubia tinctorum extract, which consists of numerous carbonyl and phenolic hydroxyl functional groups to increase adsorption of metals and chelate silver ions, and decrease the adsorption of silver ions by Ag NPs, in situ. Thus, the suggested catalyst preparation process does not require toxic reagents, additional reductants, and intricate instruments. To show the effectiveness of the plant extract in reducing and immobilizing Ag NPs, the structural, morphological, and physicochemical features of the particles are studied using Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, high-resolution transmission electron microscopy, vibrating sample magnetometry, X-ray diffraction analysis, and X-ray photoelectron spectroscopy. One of the advantages of the suggested method is to reduce the size of the magnetic NPs from 15-20 to 2-5 nm, in the presence of the extract. Additionally, the prepared Fe3O4@R. tinctorum/Ag nanocatalyst is demonstrated to exhibit a very high activity in the catalysis of the three-component reaction of aldehydes, amines, and alkynes (A3 coupling) with good to high yields of diverse propargylamines. Moreover, the nanocatalyst can be recovered several times with no considerable leaching or loss of performance.

Green synthesis of silver nanoparticles based on oil-water interface method with essential oil of orange peel and its application as nanocatalyst for A3 coupling.

Silver (Ag) nanoparticles (NPs) were prepared through a biological procedure where the essential oils of orange peel were used as a capper and reductant agent. Characterization of these Ag/EOs orange NPs was carried out using X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), UV-visible spectroscopy, and thermogravimetric analysis (TGA). These NPs were utilized as an effective heterogeneous nanocatalyst for the three-component reaction of amines, aldehydes and alkynes (A3 coupling). Different ranges with high performance were achieved for propargylamines. Moreover, the isolation and recovery of Ag/EOs orange NPs were very easy, efficient and cost effective.

In situ biogenic synthesis of Pd nanoparticles over reduced graphene oxide by using a plant extract (Thymbra spicata) and its catalytic evaluation towards cyanation of aryl halides.

An eco-friendly biosynthesized Pd NP anchored Thymbra spicata extract-modified graphene oxide (Pd NPs/rGO-T. spicata) nanohybrid material has been introduced. Initially, the herb, Thymbra spicata extract was immobilized on the surface of GO via their natural adhering capability. The polyphenolic function grafted in situ prepared RGO acted as the natural reductant of Pd precursor. The as-prepared nanocomposite (Pd NPs/rGO-T. spicata) was characterized using Fourier transform infrared (FTIR), UV-vis, X-ray diffraction (XRD), inductively coupled plasma (ICP), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), high resolution transmission electron microscopy (HRTEM), Fast Fourier Transform (FFT), Raman spectroscopy and EDX elemental mapping techniques. It has been observed that the Pd NPs with perfect crystal structure, uniform shape and size were dispersed homogeneously on the rGO surface. The material showed excellent water dispersibility due to the hydrophilicity of biomolecules attached over them, which is very essential in heterogeneous catalysis. The T. spicata contained biomolecules served as effective capping, reducing and stabilizing agents for the uniform immobilization of Pd precursors on graphene sheet surface without aggregation. The catalytic activity of this nano hybrid was assessed comprehensively in the cyanation of aryl halides with a wide range of substrates using K4[Fe(CN)6] as a cheap source of cyanide. The model reaction resulted outstanding catalytic performance with a great reusability of the catalysis.

Biosynthesis of Au nanoparticles supported on Fe3O4@polyaniline as a heterogeneous and reusable magnetic nanocatalyst for reduction of the azo dyes at ambient temperature.

In this research Au nanoparticles, supported on Fe3O4@polyaniline as a magnetic nanocatalyst, was synthesized and its performance has been evaluated to reduce Methylene Blue (MB) and Methyl Orange (MO) from aqueous solutions. Gold nanoparticles, as a nanocatalyst with excellent activity, were prepared through the reduction of Au3+ using a wild herbal extract (Allium Sp) without any toxic chemical compounds and harmful materials. The synthesized Fe3O4@PANI-Au magnetic nanocatalyst was characterized by different instruments. To investigate the effect of nanocatalyst concentration on the degradation rate of azo dyes, two different catalyst concentrations were used at ambient temperature. According to the carried out calculations, degradation reaction of azo dyes with NaBH4 in presence of the nanocatalyst is 103 to 104 times faster than degradation without using the catalyst.

Silver nanoparticles decorated on thiol-modified magnetite nanoparticles (Fe3O4/SiO2-Pr-S-Ag) as a recyclable nanocatalyst for degradation of organic dyes.

Surface modification of Fe3O4 nanoparticle with thiol groups was used for the immobilization of silver nano-particles to produce Fe3O4/SiO2-Pr-S-Ag NPs. The prepared catalyst was characterized by Inductively coupled plasma (ICP), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectrum (EDS), vibrating sample magnetometer (VSM) and Fourier transform infrared (FTIR) analysis. In this fabrication, thio-groups played an important role as a capping and stabilizing agent for Ag nanoparticles. Fe3O4/SiO2-Pr-S-Ag NPs show high catalytic activity as recyclable nanocatalyst toward degradation of 4-nitrophenol (4-NP), rhodamine B (RhB), and Methylene blue (MB) in the presence of NaBH4 in water at room temperature. With the help of UV-Vis spectroscopy, catalysis reactions were examined. Furthermore, these reactions followed the pseudo-first order rate equation.

Palladium nanoparticles decorated into a biguanidine modified-KIT-5 mesoporous structure: a recoverable nanocatalyst for ultrasound-assisted Suzuki-Miyaura cross-coupling.

In the current research work, a new KIT-5-biguanidine-Pd(0) catalyst was prepared and applied to ultrasound-assisted Suzuki-Miyaura cross-coupling reactions using ultrasound waves at ambient temperature. The ultrasound-assisted method is a green and efficient method for C-C coupling. Many parameters of the Suzuki coupling reaction were examined, such as the irradiation time, the types of organic and inorganic bases, the types of aprotic and protic solvents, and the dosage (mol%) of catalyst. Also, the results showed that the yields from the ultrasound-assisted coupling reactions were higher than from non-irradiated reactions. The prepared catalyst was characterized via HR-TEM, SEM-EDX-mapping, FT-IR, ICP-AAS, BET-BJH, and XRD studies. The stability and catalytic performance of the prepared catalyst were good, and it could be reused 6 times without catalytic activity loss for the Suzuki-Miyaura cross-coupling reaction.

Green synthesis of Pd nanoparticles supported on reduced graphene oxide, using the extract of Rosa canina fruit, and their use as recyclable and heterogeneous nanocatalysts for the degradation of dye pollutants in water.

The current study suggests a convenient synthesis of in situ, ecofriendly and well-dispersed palladium nanoparticles with narrow and small dimension distributions on a graphene oxide (GO) surface using a Rosa canina fruit extract as a stabilizer and reducing agent without the addition of any other stabilizers or surfactants. The as-synthesized nanocatalyst (Pd NPs/RGO) was assessed with XRD, UV-vis, FE-SEM, EDS, TEM, ICP and WDX. The obtained heterogeneous nanocatalyst showed catalytic performance for reducing 4-nitrophenol (4-NP), rhodamine B (RhB) and methylene blue (MB) at ambient temperature in an ecofriendly medium. The catalyst was retained by centrifugation and reused several times with no considerable change in its catalytic performance.