The role of WOx and dopants (ZrO2 and SiO2) on CeO2-based nanostructure catalysts in the selective oxidation of benzyl alcohol to benzaldehyde under ambient conditions.

Herein, the efficacy of WOx-promoted CeO2-SiO2 and CeO2-ZrO2 mixed oxide catalysts in the solvent-free selective oxidation of benzyl alcohol to benzaldehyde using molecular oxygen as an oxidant is reported. We evaluated the effects of the oxidant and catalyst concentration, reaction duration, and temperature on the reaction with an aim to optimize the reaction conditions. The as-prepared CeO2, CeO2-ZrO2, CeO2-SiO2, WOx/CeO2, WOx/CeO2-ZrO2, and WOx/CeO2-SiO2 catalysts were characterized by X-ray diffraction (XRD), N2 adsorption-desorption, Raman spectroscopy, temperature-programmed desorption of ammonia (TPD-NH3), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). These characterisation results indicated that the WOx/CeO2-SiO2 catalyst possessed improved physicochemical (i.e., structural, textural, and acidic) properties owing to the strong interactivity between WOx and CeO2-SiO2. A higher number of Ce3+ ions (Iu'''/ITotal) were created with the WOx/CeO2-SiO2 catalyst than those with the other catalysts in this work, indicating the generation of a high number of oxygen vacancies. The WOx/CeO2-SiO2 catalyst exhibited a high conversion of benzyl alcohol (>99%) and a high selectivity (100%) toward benzaldehyde compared to the other promoted catalysts (i.e., WOx/CeO2 and WOx/CeO2-ZrO2), which is attributed to the smaller particle size of the WOx and CeO2 and their high specific surface area, more significant number of acidic sites, and superior number of oxygen vacancies. The WOx/CeO2-SiO2 catalyst could be quickly recovered and utilized at least five times without suffering any appreciable activity loss.

Highly active reduced graphene oxide supported Ni nanoparticles for C-S coupling reactions.

Air-stable Ni nanoparticles (with particle size ∼ 11 nm) supported on reduced graphene oxide [Ni(0)@RGO] was prepared by a simple and easy procedure. We previously described the Kumada-Corriu C-C cross-coupling reaction between iodo-arenes and Grignard reagents with Ni(0)RGO as a stable and efficient catalyst. This Ni(0)RGO catalyst gave an excellent yield (92%) and good recyclability (up to the 5th cycle). This communication confirms that the catalyst shows superior efficacy for the C-S coupling reaction, similar to that for the Kumada-Corriu C-C cross-coupling reaction. A catalytic experiment with the Ni(0)@RGO recycled material was also performed. HRTEM study of the reused material after the C-S coupling reaction confirmed the retention of the original (fresh) catalyst structure. It is reusable up to the 7th cycle without any activity loss.

Green Synthesis of Cu Nanoparticles in Modulating the Reactivity of Amine-Functionalized Composite Materials towards Cross-Coupling Reactions.

Control over both dispersion and the particle size distribution of supported metal particles is of paramount importance for the catalytic activity of composite materials. We describe the synthesis of materials with Cu nanoparticles well-dispersed on different amine-functionalized supports, using the extract of Wallich Spurge as a green, reducing agent. Graphene oxide (GO), mesoporous silica (MCM-41), mesoporous zirconia, and reduced graphene oxide-mesoporous silica (RGO-MCM-41) were explored as supports. Cu nanoparticles were better stabilized on RGO-MCM-41 compared to other supports. The novel composite materials were characterized by X-ray diffraction (XRD), Raman spectra, Scanning electron microscope (SEM), Transmission electron microscopy analysis and HR-TEM. SEM and EDX techniques. High angle XRD confirmed the conversion of graphene oxide to reduced graphene oxide (RGO) with plant extract as a reducing agent. Both XRD and TEM techniques confirmed the Cu nanoparticle formation. The catalytic activity of all the prepared materials for the Ullmann coupling reactions of carbon-, oxygen-, and nitrogen-containing nucleophiles with iodobenzene was evaluated. From the results, 5 wt% Cu on amine-functionalized reduced graphene oxide/mesoporous silica nanocomposite (5 wt%Cu(0)-AAPTMS@RGO-MCM-41) exhibited excellent efficiency with 97% yield of the C-C coupling product in water at 80 °C in 5 h. The activity remained unaltered almost up to the fourth cycle. The Cu nanoparticles stabilized by organic amine group on RGO hybrid facilitated sustained activity.

Pd nanoparticle supported reduced graphene oxide and its excellent catalytic activity for the Ullmann C-C coupling reaction in a green solvent.

An efficient and easy route to synthesize reduced graphene oxide with well dispersed palladium (Pd) nanoparticles (Pd(0)-RGO) is described. The synthesized materials were fully characterized by different techniques such as: XRD, FTIR, Raman, SEM, and TEM. An average particle size of 7.5 nm for the metal particles was confirmed by TEM analysis. Pd(0)-RGO demonstrated outstanding catalytic activity for Ullmann coupling with 97% yield and good reusability (4 cycles).

Ni nanoparticle supported reduced graphene oxide as a highly active and durable heterogeneous material for coupling reactions.

We report the loading of highly air stable Ni(0) nanoparticles (average particle size = 11 nm) on the surface of a reduced graphene oxide (RGO) material. The material was characterized using different techniques, including Raman spectroscopy, XRD, TEM, SEM, and HRTEM analysis. The Ni(0)@RGO catalyst showed superb efficiency towards Kumada-Corriu C-C cross-coupling reactions, with 92% yield of 4-methoxybiphenyl at 60 °C. The recycled material can be reused up to the 5th cycle after regeneration by calcination, without loss of activity.

Facile Synthesis of Three-Dimensional Mg-Al Layered Double Hydroxide/Partially Reduced Graphene Oxide Nanocomposites for the Effective Removal of Pb2+ from Aqueous Solution.

A series of three-dimensional (3D) porous nanocomposites, comprised of partially reduced graphene oxide (pRGO) and CO32- containing Mg-Al layered double hydroxide, were synthesized in two steps. In the first step, graphene oxide (GO) was fabricated by a modified Hummers' method, and, subsequently, in the second step layered double hydroxide (LDH) nanosheets were homogeneously grown on the surface of the GO sheets by an in situ crystallization approach, involving a facile coprecipitation technique. The alkaline medium used for the in situ growth of LDH on the GO surface resulted in the partial reduction of GO to pRGO, which was confirmed by XRD. XRD also revealed the successful formation of crystalline LDH nanosheets on the surface of pRGO, whereas FTIR spectroscopy confirmed the presence of different functional groups in the nanocomposites. Nitrogen adsorption-desorption studies of the prepared nanocomposites revealed them as high surface area porous materials. Electron microscopic techniques, like TEM and SEM, confirmed that the architectures of the prepared nanocomposites displayed an interconnected 3D network, where a number of LDH nanosheets were interwoven on the surface of pRGO. The elemental mapping and EDX analysis qualitatively confirmed the presence of all of the expected elements in the fabricated nanocomposites. Because of the unique 3D porous network and the presence of a large number of oxygen-containing functional groups, the prepared nanocomposites proved suitable for the adsorption of Pb2+ ions from aqueous solution with a maximum adsorption capacity of 116.2 mg g-1. Equilibrium was achieved after 180 min on conducting the adsorption experiments at pH 4.5. Desorption experiments established the possibility of recovering the metal ions as well as the regeneration of adsorbents for repeated use.

Novel carbapenem chalcone derivatives: synthesis, cytotoxicity and molecular docking studies.

A one-pot efficient synthetic protocol is described for the synthesis of carbapenem chalcone derivatives using AAPTMS@MCM-41 heterogeneous catalyst. Various substituted aromatic aldehydes were attached to highly chiral and reactive carbapenem using this approach. The cytotoxic activity evaluation of all synthesized compounds was performed against lung cancer cell lines (A-549) and breast cancer cell lines (MCF-7) using the MTT assay. Among the tested compounds, compound CPC-2 showed better activity against MCF-7 cell lines with an IC50 value 2.52 µM mL(-1); whereas compound CPC-4 showed good activity against A-549 cell lines with an IC50 value 1.59 µM mL(-1). In order to support the observed activity profiles, the representative compounds were flexibly docked into the active sites of the Anaplastic Lymphoma Kinase (ALK) enzyme and the Estrogen receptor (ERß). The most active anticancer compounds exhibited stronger binding affinities for proteins.

Covalent Modification of Organo-Functionalized Graphene Oxide and its Scope as Catalyst for One-Pot Pyrazolo-Pyranopyrimidine Derivatives.

The surface of graphene oxide (GO) was modified using [3-(2-aminoethylamino)propyl]trimethoxysilane (diamine), which exhibited excellent catalytic activity for one-pot multicomponent reactions. The newly synthesized material was fully characterized by various instrumental techniques including Fourier-transfer infrared (FTIR) and Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The instrumental analysis confirmed the successful grafting of organic amine functional groups onto the graphene oxide surface. The diamine-functionalized GO proved to be an excellent catalyst for the synthesis of pyrazolo-pyranopyrimidine derivatives with 93 % yield and high selectivity. The catalytic activity almost remained unaltered up to three cycles. The newly synthesized pyrazolo-pyranopyrimidine derivatives have potential use as scaffolds in designing new pharmaceutical products.

Amine functionalized K10 montmorillonite: a solid acid-base catalyst for the Knoevenagel condensation reaction.

Different amine functionalized K10 montmorillonites were hydrothermally fabricated by a simple method of treatment of the neat clay with different amine solutions and used as heterogeneous catalysts towards the Knoevenagel condensation reaction. Catalytic results show that the di-amine functionalized K10 montmorillonite exhibits high efficacy for promoting this reaction at room temperature and in the absence of a solvent. The solid catalyst was characterized using a variety of different techniques; including Fourier transform infrared spectroscopy (FT-IR), nitrogen physisorption measurements, (29)Si CP MAS NMR spectroscopy, NH3-temperature programmed desorption (NH3-TPD), X-ray powder diffraction (XRD), and field emission scanning electron microscopy (FESEM). The catalyst could be recycled and reused for several runs without any loss of inherent catalytic activity.

A facile method for the synthesis of copper modified amine-functionalized mesoporous zirconia and its catalytic evaluation in C-S coupling reaction.

A new copper modified amine functionalized zirconia has been synthesized by a co-condensation method using zirconium butoxide and aminopropyltriethoxy-silane (APTES) in the presence of a cationic surfactant CTAB followed by impregnation of copper. Nitrogen adsorption-desorption, X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), (13)C nuclear magnetic resonance (NMR), scanning electron micrography (SEM), transmittance electron micrography (TEM), thermo gravimetric analysis-differential thermal analysis (TGA-DTA), X-ray photoelectron spectroscopy (XPS) and UV-vis DRS spectroscopic tools are used to characterize the materials. FT-IR and DRS results indicated the incorporation of Cu and amino groups on the surface of zirconia. This Cu-anchored mesoporous material acts as an efficient, reusable catalyst in the aryl-sulfur coupling reaction between aryl iodide and thiophenol for the synthesis of value added diarylsulfides.

Cesium salts of heteropoly acid immobilized mesoporous silica: an efficient catalyst for acylation of anisole.

A series of Cs salt of phosphotungstic acid (Cs-PTA) supported on MCM-41 (Cs-PTA/MCM-41) was synthesized by a wet impregnation method and thoroughly characterized by using various analytical techniques, viz. X-ray diffraction, UV-Vis diffused reflectance spectroscopy (UV-Vis DRS), nitrogen adsorption desorption, scanning electron microscopy (SEM), Infrared spectra (FTIR), temperature programmed reduction (TPR), and temperature programmed desorption (TPD). The spectroscopic results revealed that Cs-PTA is highly dispersed on a MCM-41 surface. The 50 wt.% Cs-PTA supported on MCM-41 showed remarkable catalytic performance toward acylation of anisole reaction. The catalyst is regenerable by simple calcinations without appreciable loss in catalytic activity.