Polyethylene glycol-modified mesoporous zerovalent iron nanoparticle as potential catalyst for improved reductive degradation of Congo red from wastewater.

In this study, bare zero-valent iron nanoparticles (nZVI) have been modified using polyethylene glycol (PEG) of various molecular weight in a facile technique. The synthesized nZVI modified with PEG, M.W. of 600 and 6000 was denoted by nZVI-PEG600 and nZVI-PEG6000, respectively, and compared their catalytic activity towards the reductive degradation of Congo red (CR) using NaBH4.The existence of PEG layer surrounds the nZVI core was confirmed by several characterization tools, such as XRD, FTIR, FESEM and TEM. Herein, both nZVI-PEG600 and nZVI-PEG6000 exhibited remarkable removal efficiencies of 89.6% and 99.2% within 14 min of reaction time. The optimum reaction parameters were found to be as follows: 0.2 g L-1 catalyst dose and initial dye concentration of 2 × 10-5 molL-1 etc. Kinetic studies of dye degradation were investigated which follow pseudo-1st-order kinetics. The TOC analysis confirmed the complete mineralization of CR dye by nZVI-PEG6000 nanocatalyst. GCMS analysis of plausible degraded products was performed to elucidate a probable mechanistic pathway of CR degradation. Further, we have investigated the degradation of two anionic dyes mixture, i.e., CR and methyl orange (MO) using best catalyst, i.e., nZVI-PEG6000.

Cost-effective synthesis method of facile environment friendly SnO2 nanoparticle for efficient photocatalytic degradation of water contaminating compound.

The present study demonstrates an intensive experimental work based on the tin oxide (SnO2) nanoparticle synthesis which was successfully carried out by a simple conventional precipitation method followed by calcination at 700 °C. The synthesized nanoparticles were characterized by X-ray powder diffraction (XRD), UV-Vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM) and energy-dispersive X-ray spectroscopy (EDAX). The XRD pattern proves that tetragonal rutile structure SnO2 nanoparticles were formed. The crystallite particle size calculation from Scherer's equation revealed the average size of 28.5 nm. The absorption spectrum of SnO2 nanoparticles showed absorption band at about 290 nm and the band gap energy (Eg) from Tauc plot was obtained at 3.8 eV. The photocatalytic degradation of pharmaceutical compound, 4-aminopyridine (5 ppm) using synthesized SnO2 nanoparticle, was assessed. The effect of variable catalyst dosage, pH and irradiation sources, were studied. The optimum catalyst dosage and pH were found to be 1.5 gm/L and 6.5, respectively. The degradation efficiency of water contaminant 4-aminopyridine under UV light and solar light irradiation for 120 min were found to be 97% and 11%, respectively. The reusability of the catalyst was checked and has been found stable after three photocatalytic runs.

Alkali metal ion induced cube shaped mesoporous hematite particles for improved magnetic properties and efficient degradation of water pollutants.

Mesoporous cube shaped hematite (α-Fe2O3) particles were prepared using FeCl3 as an Fe(3+) precursor and 1-butyl-3-methylimidazolium bromide (ionic liquid) as a soft template in the presence of different alkali metal (lithium, sodium and potassium) acetates, under hydrothermal conditions at 150 °C/4 h followed by calcination at 350 °C. The formation of the α-Fe2O3 phase in the synthesized samples was confirmed by XRD, FTIR and Raman spectroscopy. Unlike K(+) ions, intercalation of Li(+) and Na(+) ions occurred in α-Fe2O3 crystal layers as evidenced by XRD and Raman spectroscopy. Electron microscopy (FESEM and TEM) images showed the formation of cube-like particles of different sizes in the presence of Li(+), Na(+) and K(+) ions. The mesoporosity of the products was confirmed by N2 adsorption-desorption studies, while their optical properties were analyzed by UV-DRS. Na(+) ion intercalated α-Fe2O3 microcubes showed improved coercivity (5.7 kOe) due to increased strain in crystals, and shape and magnetocrystalline anisotropy. Temperature dependent magnetization of the samples confirmed the existence of Morin temperature in the range of 199-260 K. Catalytic degradation of methylene blue (MB), a toxic water pollutant, was studied using the synthesized products via a heterogeneous photo-Fenton process. The degradation products were traced by electrospray ionization-mass spectrometry (ESI-MS). The α-Fe2O3 microcubes obtained in the presence of Na(+) ions exhibited a more efficient degradation of MB to non-toxic open chain products.

Bi-template assisted synthesis of mesoporous manganese oxide nanostructures: Tuning properties for efficient CO oxidation.

A simple soft bi-templating process was used for the synthesis of mesoporous manganese oxide nanostructures using KMnO4 as a precursor and polyethylene glycol and cetyltrimethylammonium bromide as templates in the presence of benzaldehyde as an organic additive in alkaline media, followed by calcination at 400 °C. X-ray diffraction and Raman spectroscopic analysis of the calcined products confirmed the existence of stoichiometric (MnO2 and Mn5O8) and non-stoichiometric mixed phases (MnO2 + Mn5O8) of Mn oxides obtained by tuning the concentration of the additive and the synthesis time. The surface properties of the prepared Mn oxides were determined by X-ray photoelectron spectroscopy. The mesoporosity of the samples was confirmed by N2 adsorption-desorption. Different synthetic conditions resulted in the formation of different morphologies of the Mn oxides (α-MnO2, Mn5O8, and α-MnO2 + Mn5O8), such as nanoparticles, nanorods, and nanowires. The synthesized mesoporous Mn oxide nanostructures were used for the catalytic oxidation of the harmful air pollutant carbon monoxide. The Mn5O8 nanoparticles with the highest Brunauer-Emmett-Teller surface area and the non-stoichiometric manganese oxide (α-MnO2 + Mn5O8) nanorods with a higher Mn(3+) concentration had the best catalytic efficiency.

Ligand-assisted soft-chemical synthesis of self-assembled different shaped mesoporous Co3O4: efficient visible light photocatalysts.

Mesoporous self-assembled cobalt oxide (Co3O4) of different shapes was synthesized by a facile soft-chemical process using cobalt nitrate, oxalic acid and phosphoric acid in the presence of cationic templates, cetyltrimethylammonium bromide, 1-butyl-3-methylimidazolium bromide, and pyridinium bromide at 75 °C/2 h followed by calcination at 300 °C. The effect of cationic templates of the samples on the physico-chemical properties, and the photocatalytic efficiency for the degradation of Chicago Sky Blue 6B was studied. Pyridinium bromide and 1-butyl-3-methylimidazolium bromide facilitated formation of particles with different shaped morphology compared to cetyltrimethylammonium bromide. The rod-like particles having higher surface area exhibited higher photocatalytic performance.

Synthesis of morphology controllable porous Co3O4 nanostructures with tunable textural properties and their catalytic application.

Porous cobalt oxide (Co3O4) nanorod (50-100 nm) and nanosheet-like (70-100 nm) particles were synthesized by a facile hydrothermal method at 150 °C for 2-5 h and 12-24 h, respectively, using aqueous-based precursors like cobalt nitrate, urea and water in the absence of any templating agents followed by their calcination at 300 °C. Morphology and textural properties were tuned by changing the synthesis time at 150 °C. A 3D architecture of Co3O4 was formed by the self-assembly of nanostructured (nanorod and nanosheet) particles. The BET surface area, pore volume and pore diameter of the sample prepared at 150 °C for 5 h were 112 m(2) g(-1), 0.5 cm(3) g(-1) and 7.4 nm, respectively, and it exhibited the highest catalytic performance with a rate constant of 56.8 × 10(-3) min(-1) for the degradation of Chicago Sky Blue 6B, a carcinogenic azo dye used in the textile, paper and food industries. Rod-like particles with a mesoporous structure rendered a better catalytic efficiency than sheet-like particles having both microporous and mesoporous structures. An interrelationship amongst the morphology, textural properties and the catalytic efficiency of Co3O4 was established.

Solvent-adoptable polymer Ni/NiCo alloy nanochains: highly active and versatile catalysts for various organic reactions in both aqueous and nonaqueous media.

The synthesis of solvent-adoptable monometallic Ni and NiCo alloy nanochains by a one-pot solution phase reduction method in the presence of poly(4-vinylphenol) (PVPh) is demonstrated. The elemental compositions of the as-prepared alloys are determined by inductively coupled plasma optical emission spectroscopy (ICP-OES) and energy-dispersive X-ray spectroscopy (EDS), which are matching well with the target compositions. The morphology analysis by TEM and FESEM confirms that the nanochains are made up of organized spherical monometallic Ni or bimetallic NiCo alloy nanoparticles (NPs). However, there is no nanochain formation when the alloy is prepared without the polymer PVPh. A possible mechanism for the formation of such NiCo alloy nanochains is discussed. The X-ray diffraction and selected area electron diffraction patterns reveal that the Ni/NiCo alloys are polycrystalline with fcc structure. The obtained Ni or NiCo alloy nanostructures are ferromagnetic with very high coercivity. The polymer Ni/NiCo alloy nanochains are dispersible in both water and organic media that makes them versatile enough to use as catalysts in the reactions carried out in both types of media. The catalytic activities of these Ni/NiCo alloy nanochains are extremely high in the borohydride reduction of p-nitrophenol in water. In organic solvents, these nanochains can act as efficient catalysts, under ligand-free condition, for the C-S cross-coupling reactions of various aryl iodides and aryl thiols for obtaining the corresponding cross-coupled products in good to excellent yield up to 96%. The NiCo nanochain also successfully catalyzes the C-O cross-coupling reaction in organic medium. A possible mechanism for NiCo alloy nanochain-catalyzed cross-coupling reaction is proposed.