Synthesis of Nanoparticulate Alloys of the Composition Cu2Zn(1-x)Fe(x)SnS4: Structural, Optical, and Magnetic Properties.

Nanoparticles of the semiconductor Cu2Zn(1-x)Fe(x)SnS4 with different mole fractions of iron (x(Fe)) were synthesized by the decomposition of molecular precursors in oleylamine. The composition, structure, optical, and magnetic properties of the nanoparticles are reported. The parent (Cu2ZnSnS4) zinc material is usually reported as kesteritic and the corresponding iron phase as stannitic; with different site occupancies and tetragonalities. In the small ca. 8-10 nm particles prepared, the smooth variation in lattice parameters and other measured properties suggest that the phase change, with composition, may be absent. SQUID magnetometry suggests that the iron containing samples are ferromagnetic at 5 K and paramagnetic at 300 K.

In Situ synthesis of self-assembled gold nanoparticles on glass or silicon substrates through reactive inkjet printing.

A facile and low cost method for the synthesis of self-assembled nanoparticles (NPs) with minimal size variation and chemical waste by using reactive inkjet printing was developed. Gold NPs with diameters as small as (8±2) nm can be made at low temperature (120 °C). The size of the resulting NPs can be readily controlled through the concentration of the gold precursor and oleylamine ink. The pure gold composition of the synthesized NPs was confirmed by energy-dispersive X-ray spectroscopy (EDXS) analysis. High-resolution SEM (HRSEM) and TEM (HRTEM), and X-ray diffraction revealed their size and face-centered cubic (fcc) crystal structure, respectively. Owing to the high density of the NP film, UV/Vis spectroscopy showed a red shift in the intrinsic plasmonic resonance peak. We envision the extension of this approach to the synthesis of other nanomaterials and the production of tailored functional nanomaterials and devices.

Molybdenum disulfide (MoS2) along with graphene nanoplatelets (GNPs) utilized to enhance the capacitance of conducting polymers (PANI and PPy).

Hybrid composites of molybdenum disulfide (MoS2), graphene nanoplatelets (GNPs) and polyaniline (PANI)/polypyrrole (PPy) have been synthesized as cost-effective electrode materials for supercapacitors. We have produced MoS2 from molybdenum dithiocarbamate by a melt method in an inert environment and then used a liquid exfoliation method to form its composite with graphene nanoplatelets (GNPs) and polymers (PANI and PPy). The MoS2 melt/GNP ratio in the resultant composites was 1 : 3 and the polymer was 10% by wt. of the original composite. XRD (X-ray diffraction analysis) confirmed the formation of MoS2 and SEM (scanning electron microscopy) revealed the morphology of the synthesized materials. The electrochemical charge storage performance of the synthesized composite materials was assessed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge (GCCD) measurements. Resultant composites showed enhanced electrochemical performances (specific capacitance = 236.23 F g-1, energy density = 64.31 W h kg-1 and power density = 3858.42 W kg-1 for MoS2 melt 5 mPP at a current density of 0.57 A g-1 and had 91.87% capacitance retention after 10 000 charge-discharge cycles) as compared to the produced MoS2; thus, they can be utilized as electrode materials for supercapacitors.

A single-source precursor route to unusual PbSe nanostructures by a solution-liquid-solid method.

PbSe nanowires (NWs) have been synthesized by using a single-source precursor route. Carefully controlling the conditions of individual reactions leads to PbSe NWs with well-defined diameters (8-25 nm) and lengths (100 nm-1 µm). The as-grown PbSe NWs are highly crystalline, defect free, and readily dispersible in organic solvents. The NWs have been characterized by X-ray diffraction and high-resolution transmission electron microscopy.

Phyto-synthesized facile Pd/NiOPdO ternary nanocomposite for electrochemical supercapacitor applications.

Sustainable and effective electrochemical materials for supercapacitors are greatly needed for solving the global problems of energy storage. In this regard, a facile nanocomposite of Pd/NiOPdO was synthesized using foliar phyto eco-friendly agents and examined as an electrochemical electrode active material for supercapacitor application. The nanocomposite showed a mixed phase of a ternary nano metal oxide phase of rhombohedral NiO and tetragonal PdO confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and XPS (X-rays photoelectron spectroscopy). The optical (direct) energy value of the synthesized nanocomposite was 3.14 eV. The phyto-functionalized nanocomposite was studied for electrochemical supercapacitor properties and revealed a specific capacitance of 88 F g-1 and low internal resistance of 0.8 Ω. The nanoscale and phyto organic species functionalized nanocomposite exhibited enhanced electrochemical properties for supercapacitor application.

Facile ZnO-based nanomaterial and its fabrication as a supercapacitor electrode: synthesis, characterization and electrochemical studies.

In recent times, tremendous efforts have been devoted to the efficient and cost-effective advancements of electrochemically active metal oxide nanomaterials. Here, we have synthesized a facile nanomaterial of ZnO@PdO/Pd by employing extracted fuel from E. cognata leaves following a hydrothermal route. The phyto-fueled ZnO@PdO/Pd nanomaterial was fabricated into a supercapacitor electrode and was scrutinized by galvanostatic charge-discharge, electrochemical impedance spectroscopy and cyclic voltammetry to evaluate its energy storage potential, and transport of electrons and conductivity. Substantial specific capacitance i.e., 178 F g-1 was obtained in the current study in aKOH electrolyte solution. A specific energy density of 3.7 W h Kg-1 was measured using the charge-discharge data. A high power density of 3718 W Kg-1 was observed for the ZnO@PdO/Pd electrode. Furthermore, the observed low internal resistance of 0.4 Ω suggested effective electron- and ion diffusion. Thus, the superb electrochemical behavior of the ZnO@PdO/Pd nanocomposite was exposed, as verified by the significant redox behavior shown by cyclic voltammetry and galvanostatic charge-discharge.

Impedance Spectroscopic Study of Nickel Sulfide Nanostructures Deposited by Aerosol Assisted Chemical Vapor Deposition Technique.

This research aims to synthesize the Bis(di-isobutyldithiophosphinato) nickel (II) complex [Ni(iBu2PS2)] to be employed as a substrate for the deposition of nickel sulfide nanostructures, and to investigate its dielectric and impedance characteristics for applications in the electronic industry. Various analytical tools including elemental analysis, mass spectrometry, IR, and TGA were also used to further confirm the successful synthesis of the precursor. NiS nanostructures were grown on the glass substrates by employing an aerosol assisted chemical vapor deposition (AACVD) technique via successful decomposition of the synthesized complex under variable temperature conditions. XRD, SEM, TEM, and EDX methods were well applied to examine resultant nanostructures. Dielectric studies of NiS were carried out at room temperature within the 100 Hz to 5 MHz frequency range. Maxwell-Wagner model gave a complete explanation of the variation of dielectric properties along with frequency. The reason behind high dielectric constant values at low frequency was further endorsed by Koops phenomenological model. The efficient translational hopping and futile reorientation vibration caused the overdue exceptional drift of ac conductivity (σac) along with the rise in frequency. Two relaxation processes caused by grains and grain boundaries were identified from the fitting of a complex impedance plot with an equivalent circuit model (Rg Cg) (Rgb Qgb Cgb). Asymmetry and depression in the semicircle having center present lower than the impedance real axis gave solid justification of dielectric behavior that is non-Debye in nature.

Impedance Spectroscopy Analysis of PbSe Nanostructures Deposited by Aerosol Assisted Chemical Vapor Deposition Approach.

This research endeavor aimed to synthesize the lead (II) diphenyldiselenophosphinate complex and its use to obtain lead selenide nanostructured depositions and further the impedance spectroscopic analysis of these obtained PbSe nanostructures, to determine their roles in the electronics industry. The aerosol-assisted chemical vapor deposition technique was used to provide lead selenide deposition by decomposition of the complex at different temperatures using the glass substrates. The obtained films were revealed to be a pure cubic phase PbSe, as confirmed by X-ray diffraction analysis. SEM and TEM micrographs demonstrated three-dimensionally grown interlocked or aggregated nanocubes of the obtained PbSe. Characteristic dielectric measurements and the impedance spectroscopy analysis at room temperature were executed to evaluate PbSe properties over the frequency range of 100 Hz-5 MHz. The dielectric constant and dielectric loss gave similar trends, along with altering frequency, which was well explained by the Koops theory and Maxwell-Wagner theory. The effective short-range translational carrier hopping gave rise to an overdue remarkable increase in ac conductivity (σac) on the frequency increase. Fitting of a complex impedance plot was carried out with an equivalent circuit model (Rg Cg) (Rgb Qgb Cgb), which proved that grains, as well as grain boundaries, are responsible for the relaxation processes. The asymmetric depressed semicircle with the center lower to the impedance real axis provided a clear explanation of non-Debye dielectric behavior.

Organic template-assisted green synthesis of CoMoO4 nanomaterials for the investigation of energy storage properties.

Transitional metal oxide nanomaterials are considered to be potential electrode materials for supercapacitors. Therefore, in the past few decades, huge efforts have been devoted towards the sustainable synthesis of metal oxide nanomaterials. Herein, we report a synergistic approach to synthesize spherical-shaped CoMoO4 electrode materials using an inorganic-organic template via the hydrothermal route. As per the synthesis strategy, the precursor solution was reacted with the organic compounds of E. cognata to tailor the surface chemistry and morphology of CoMoO4 by organic species. The modified CoMoO4 nanomaterials revealed a particle size of 23 nm by X-ray diffraction. Furthermore, the synthesized material was scrutinized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, field emission scanning electron microscopy and energy dispersive spectroscopy. The optical band gap energy of 3.6 eV was calculated by a Tauc plot. Gas chromatography-mass spectrometry identified cyclobutanol (C4H8O) and octodrine (C8H19N) as the major stabilizing agents of the CoMoO4 nanomaterial. Finally, it was revealed that the bioorganic framework-derived CoMoO4 electrode exhibited a capacitance of 294 F g-1 by cyclic voltammetry with a maximum energy density of 7.3 W h kg-1 and power density of 7227.525 W kg-1. Consequently, the nanofeatures and organic compounds of E. cognata were found to enhance the electrochemical behaviour of the CoMoO4-fabricated electrode towards supercapacitor applications.

Organic template-based ZnO embedded Mn3O4 nanoparticles: synthesis and evaluation of their electrochemical properties towards clean energy generation.

To deal with fossil fuel depletion and the rise in global temperatures caused by fossil fuels, cheap and abundant materials are required, in order to fulfill energy demand by developing high-performance fuel cells and electrocatalysts. In this work, a natural organic agent has been used to synthesize nano-structured ZnO/Mn3O4 with high surface area and enhanced electrocatalytic performance. Upon pre-annealing treatment, mixed metal oxide precipitates are formed due to the complex formation between a metal oxide and organic extract. The thermally annealed mixed oxide ZnO/Mn3O4 was characterized by XRD diffractometer, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). Gas chromatography-mass spectrometry (GC-MS) identified methyldecylamine as a major stabilizing agent of the synthesized nanomaterial. Using a Tauc plot, the calculated band energy for the synthesized ZnO/Mn3O4 mixed metal oxide was 1.65 eV. Moreover, we have demonstrated the effects of incorporated organic compounds on the surface chemistry, morphology and electrochemical behavior of ZnO/Mn3O4. The phyto-functionalized ZnO/Mn3O4 was deposited on Ni-foam for electrocatalytic studies. The fabricated electrode revealed good performance with low over-potential and Tafel slope, suggesting it to be suitable as a potential catalyst for water splitting application, in particular for the oxygen evolution reaction (OER). The overall findings of the current study provide a cost-effective and efficient organic template for functionalization and sustainable fabrication of ZnO/Mn3O4 nanomaterial for application as an electrocatalyst.

Phyto-inspired and scalable approach for the synthesis of PdO-2Mn2O3: a nano-material for application in water splitting electro-catalysis.

A modified co-precipitation method has been used for the synthesis of a PdO-2Mn2O3 nanocomposite as an efficient electrode material for the electro-catalytic oxygen evolution (OER) and hydrogen evolution reaction (HER). Palladium acetate and manganese acetate in molar ratio 1 : 4 were dissolved in water, and 10 ml of an aqueous solution of phyto-compounds was slowly added until completion of precipitation. The filtered and dried precipitates were then calcined at 450 °C to obtain a blackish brown colored mixture of PdO-2Mn2O3 nanocomposite. These particles were analyzed by ultra violet visible spectrophotometry (UV-vis), infrared spectroscopy (FTIR), powder X-ray diffractometry (XRD), scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) for crystallinity, optical properties, and compositional and morphological makeup. Using Tauc's plot, the direct band gap (3.18 eV) was calculated from the absorption spectra. The average crystallite sizes, as calculated from the XRD, were found to be 15 and 14.55 nm for PdO and Mn2O3, respectively. A slurry of the phyto-fabricated PdO-2Mn2O3 powder was deposited on Ni-foam and tested for electro-catalytic water splitting studies in 1 M KOH solution. The electrode showed excellent OER and HER performance with low over-potential (0.35 V and 121 mV) and Tafel slopes of 115 mV dec-1 and 219 mV dec-1, respectively. The outcomes obtained from this study provide a direction for the fabrication of a cost-effective mixed metal oxide based electro-catalyst via an environmentally benign synthesis approach for the generation of clean energy.

Structural investigations of SnS1-xSex solid solution synthesized from chalcogeno-carboxylate complexes of organo-tin by colloidal and solvent-less routes.

Tin chalcogenides are important semiconducting materials due to their non-toxic nature, cost effectiveness and layered structure. In this study, a facile synthetic route has been employed for the synthesis of a bis(selenobenzoato)dibutyltin(iv) complex, and used along with the bis(thiobenzoato)dibutyltin(iv) complex, as single source precursors, to prepare binary tin chalcogenides and their solid solution (SnS1-xSex) in the entire range. The synthesis of the solid solution was carried out by colloidal and melt methods. The comparative analysis of the solid solution obtained from both routes indicates that the colloidal method provides superior control over composition. The UV-Vis-NIR analysis showed a gradual change in the band gap, while moving from SnS to SnSe.

Bis(selenobenzoato)dibutyltin(iv) as a single source precursor for the synthesis of SnSe nanosheets and their photo-electrochemical study for water splitting.

A new organo-tin complex has been synthesized and used as a single source precursor for the synthesis of SnSe nanosheets by the hot injection method and thin films by the aerosol assisted chemical vapor deposition (AACVD) method. The films were deposited on glass substrates at three different temperatures. The textural quality and preferential growth were found to be significantly altered by changes in the deposition temperature. Oleylamine capped nanosheets and the as-deposited thin films by AACVD were characterized by powder X-ray diffraction (p-XRD) and microscopic techniques. The thin films were also studied by Raman spectroscopy. The stoichiometry is marginally affected by temperature, and all films were slightly selenium deficient. The synthesized material was also evaluated for the photoelectrochemical (PEC) splitting of water. The PEC study revealed the bifunctional nature of the material, which can be applied for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), by switching the applied potential.

4-(2-Methoxy-phenyl)-3-(3,4,5-tri-methoxy-phen-ethyl)-2H-1,2,4-triazole-5(4H)-thione.

The title compound, C(20)H(23)N(3)O(4)S, is an important biologically active heterocyclic compound. The five-membered ring is oriented with respect to the six-membered rings at dihedral angles of 78.60 (3) (trimethoxyphenyl ring) and 71.57 (3)° (methoxyphenyl ring). In the crystal structure, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into infinite chains along the c axis.

Assembly of Submicron Sized Ag, Co, and Ni Particles Into Thin Films at Liquid/Liquid Interfaces.

Submicron sized particles of Ag, Co and Ni were synthesised by reducing metal salts in ethylene glycol (EG) in the presence of polyvinylpyrrolidone (PVP). These particles on dispersion in water when held in contact with a toluene layer were found to assemble into dense films extending over large areas at the interface between the two liquids. The effect of reaction conditions (solvent, precursor concentration, temperature) on the synthesis and assembly of the particles was studied. The characteristics of the interfacial deposits and the particulate dispersions were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), ultraviolet-visible (UV-Vis) spectroscopy and dynamic light scattering (DLS).

Heterocyclic dithiocarbamato-iron(III) complexes: single-source precursors for aerosol-assisted chemical vapour deposition (AACVD) of iron sulfide thin films.

Tris-(piperidinedithiocarbamato)iron(III) (1) and tris-(tetrahydroquinolinedithiocarbamato)iron(iii) (2) complexes have been synthesized and their single-crystal X-ray structures were determined. Thermogravimetric analysis (TGA) of the complexes showed decomposition to iron sulfide. Both complexes were then used as single-source precursors for the deposition of iron sulfide thin films by aerosol-assisted chemical vapour deposition (AACVD). Energy-dispersive X-ray (EDX) spectroscopy confirmed the formation of iron sulfide films. The addition of tert-butyl thiol almost doubled the sulfur content in the deposited films. Scanning electron microscopy (SEM) images of the iron sulfide films from both complexes showed flakes/leaves/sheets, spherical granules and nanofibres. The sizes and shapes of these crystallites depended on the nature of the precursor, temperature, solvent and the amount of tert-butyl thiol used. The observed optical properties are dependent upon the variation of reaction parameters such as temperature and solvent. Powder X-ray diffraction (p-XRD) studies revealed that pyrrhotite, hexagonal (Fe0.975S), marcasite and smythite (Fe3S4) phases were differently deposited.

Facile synthesis of phosphine free ultra-small PbSe nanocrystals and their light harvesting studies in ETA solar cells.

Ultra-small PbSe nanocrystals (NCs) were synthesized via a 'one-pot' approach in olive oil as the reaction medium and capping agent. The optical spectra showed discernible blue shifts in the absorption band edges (570-780 nm) due to strong quantum confinement effects and photoluminescence (PL) spectra showed significant strong emission peaks in the range of 780-850 nm. The broad peaks in the powder X-ray diffraction (p-XRD) pattern indicate the ultra-small size of the as-prepared NCs. These NCs were used to construct an extremely thin absorber (ETA) solar device after surface modification. The preliminary results indicate their potential as light harvesting entities in nanostructure based solar cells.

The synthesis, spectroscopy and X-ray single crystal structure of catena-[(µ-anacardato)-copper(II)bipyridine][Cu2{(µ-O2CC6H3(o-OH)(o-C15H31)}4(NC5H5)2].

Hydrogenation of crude anacardic acid gave a transparent crystalline product on recrystallization. When reacted with copper nitrate in the presence of pyridine it produced green crystals of a pyridine adduct of a dimeric copper(II) anacardate with the copper acetate structure. The X-ray single crystal structures of both anacardic acid and the copper complex were determined. Magnetic studies have confirmed strong antiferromagnetic coupling between copper(II) centre in the dimer. The exchange coupling constant was determined to be J = -324 cm(-1). The EPR spectra of the polycrystalline product are consistent with spin S = 1. The zero-field splitting parameter and g tensor values are |D| = 0.36 cm(-1), g(||) = 2.36 and g(⊥) = 2.06.

Single source molecular precursor routes to lead chalcogenides.

The use of single-source molecular precursors for lead chalcogenide thin films by CVD or as nanoparticles by solution methods is reviewed. The potential applications of these materials in solar energy are discussed along with the relative advantages of the various methods.