Tunability of monodispersed intermetallic AuCu nanoparticles through understanding of reaction pathways

Synthesis of size selective monodispersed nanoparticles particularly intermetallic with well-defined compositions represents a challenge. This paper presents a way for the synthesis of intermetallic AuCu nanoparticles as a model system. We show that reduction of Au and Cu precursors is sensitive to the ratio of total molar concentrations of surfactant to metal precursors. A careful design of experiments to understand the kinetics of the reduction process reveals initial formation of seed nanoparticles of pure Au. Reduction of Cu occurs on the surface of the seed followed by diffusion to yield AuCu. This understanding allows us to develop a two step synthesis where the precise size controlled seed of Au nanoparticles produced in the first step is used in the second step reaction mixture as an Au precursor to allow deposition and interdiffusion of Cu that yields size selected AuCu intermetallics of sub 10 nm sizes.

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

Two novel triads based on a diketopyrrolopyrrole (DPP) central core and two 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) units attached by thiophene rings have been synthesised having high molar extinction coefficients. These triads were characterised and used as donor materials in small molecule, solution processable organic solar cells. Both triads were blended with PC71BM as an acceptor in different ratios by wt% and their photovoltaic properties were studied. For both the triads a modest photovoltaic performance was observed, having an efficiency of 0.65%. Moreover, in order to understand the ground and excited state properties and vertical absorption profile of DPP and BODIPY units within the triads, theoretical DFT and TDDFT calculations were performed.

Morphological Evolution in Air-Stable Metallic Iron Nanostructures and Their Magnetic Study

Iron nanostructures with morphology ranging from discrete nanoparticles to nearly monodisperse hierarchical nanostructures have been successfully synthesized using solvated metal atom dispersion (SMAD) method. Such a morphological evolution was realized by tuning the molar ratio of ligand to metal. Surface energy minimization in confluence with strong magnetic interactions and ligand-based stabilization results in the formation of nanospheres of iron. The as-prepared amorphous iron nanostructures exhibit remarkably high coercivity in comparison to the discrete nanoparticles and bulk counterpart. Annealing the as-prepared amorphous Fe nanostructures under anaerobic conditions affords air-stable carbon-encapsulated Fe(0) and Fe3C nanostructures with retention of the morphology. The resulting nanostructures were thoroughly analyzed by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and Raman spectroscopy. TGA brought out that Fe3C nanostructures are more robust toward oxidation than those of a-Fe. Finally, detailed magnetic studies were carried out by superconducting quantum interference device (SQUID) magnetometer and it was found that the magnetic properties remain conserved even upon exposure of the annealed samples to ambient conditions for months.

Modulation of Electronic and Self-Assembly Properties of a Donor-Acceptor-Donor-Based Molecular Materials via Atomistic Approach

The performance of molecular materials in optoelectronic devices critically depends upon their electronic properties and solid-state structure. In this report, we have synthesized sulfur and selenium based (T4BT and T4BSe) donor-acceptor-donor (D-A-D) organic derivatives in order to understand the structure-property correlation in organic semiconductors by selectively tuning the chalcogen atom. The photophysical properties exhibit a significant alteration upon varying a single atom in the molecular structure. A joint theoretical and experimental investigation suggests that replacing sulfur with selenium significantly reduces the band gap and molar absorption coefficient because of lower electronegativity and ionization potential of selenium. Single-crystal X-ray diffraction analysis showed differences in their solid-state packing and intermolecular interactions. Subsequently, difference in the solid-state packing results variation in self-assembly. Micorstructural changes within these materials are correlated to their electrical resistance variation, investigated by conducting probe atomic force microscopy (CP-AFM) measurements. These results provide useful guidelines to understand the fundamental properties of D-A-D materials prepared by atomistic modulation.

Orotic acid as a useful supramolecular synthon for the fabrication of an OPV based hydrogel: stoichiometry dependent injectable behavior

A facile hydrogelation of a p-pyridylenevinylene derivative (PV) bearing oxyethylene chains in the presence of orotic acid (OA) occurs via various non-covalent interactions. Depending on the PV: OA molar ratio, the hydrogel shows vesicle to either cluster-type aggregate or fiber transformation. Visual color tuning, stimuli-responsiveness and injectable properties of the hydrogel are also observed.

Self-assembled ZnO nanoparticles on ZnO microsheet: ultrafast synthesis and tunable photoluminescence properties

We report on the tunable photoluminescence characteristics of porous ZnO microsheets fabricated within 1-5 min of microwave irradiation in the presence of a capping agent such as citric acid, and mixture of citric acid with polyvinylpyrrolidone (PVP). The UV emission intensity reduces to 60% and visible emission increases tenfold when the molar concentration of citric acid is doubled. Further diminution of the intensity of UV emission (25%) is observed when PVP is mixed with citric acid. The addition of nitrogen donor ligands to the parent precursor leads to a red shift in the visible luminescence. The deep level emission covers the entire visible spectrum and gives an impression of white light emission from these ZnO samples. The detailed luminescence mechanism of our ZnO samples is described with the help of a band diagram constructed by using the theoretical models that describe the formation energy of the defect energy levels within the energy band structure. Oxygen vacancies play the key role in the variation of the green luminescence in the ZnO microsheets. Our research findings provide an insight that it is possible to retain the microstructure and simultaneously introduce defects into ZnO. The growth of the ZnO microsheets may be due to the self assembly of the fine sheets formed during the initial stage of nucleation.

Effect of ultra-fast mixing in a microchannel due to a soft wall on the room temperature synthesis of gold nanoparticles

The room-temperature synthesis of mono-dispersed gold nanoparticles, by the reduction of chlorauric acid (HAuCl4) with tannic acid as the reducing and stabilizing agent, is carried out in a microchannel. The microchannel is fabricated with one soft wall, so that there is a spontaneous transition to turbulence, and thereby enhanced mixing, when the flow Reynolds number increases beyond a critical value. The objective of the study is to examine whether the nanoparticle size and polydispersity can be modified by enhancing the mixing in the microchannel device. The flow rates are varied in order to study nanoparticle formation both in laminar flow and in the chaotic flow after transition, and the molar ratio of the chlorauric acid to tannic acid is also varied to study the effect of molar ratio on nanoparticle size. The formation of gold nanoparticles is examined by UV-visual spectroscopy and the size distribution is determined using scanning electron microscopy. The synthesized nanoparticles size decreases from a parts per thousand yen6 nm to a parts per thousand currency sign4 nm when the molar ratio of chlorauric acid to tannic acid is increased from 1 to 20. It is found that there is no systematic variation of nanoparticle size with flow velocity, and the nanoparticle size is not altered when the flow changes from laminar to turbulent. However, the standard deviation of the size distribution decreases by about 30% after transition, indicating that the enhanced mixing results in uniformity of particle size.

Spectrophotometric determination of molybdenum with Syzygium jambolanum DC leaf extracts

A new spectrophotometric method for the determination of molybdenum in industrial materials has been developed using the leaf extract of Syzygium jambolanum DC based on the reaction of Mo (VI) at pH 7.0 to produce an orange-yellow complex with an absorption maximum at 426 nm. The molar absorptivity of the complex is 4.27 x 10(4) l mol(-1) cm(-1) and the absorbance, is linear in the range 0.05-0.8 ppm. Sandell sensitivity coefficient was found to be 2.25 x 10(-3) mu g/cm(2). The method is ten times more sensitive than the aqueous thiocyanate system. It has been applied successfully in micronutrient fertilizer, artificial freshwater and sea-water analyses.

Efficient visible light photocatalytic activity and enhanced stability of BiOBr/Cd(OH)(2) heterostructures

Novel BioBr/Cd(OH)(2) heterostructures were synthesized by a facile chemical bath method under ambient conditions. A series of BiOBr/Cd(OH)(2) heterostructures were obtained by tuning the Bi/Cd molar ratios. The obtained heterostructures were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). Optical properties were studied by UV-visible spectroscopy, diffuse reflectance spectroscopy and photoluminescence (PL). Photocatalytic studies on rhodamine B (RhB) under visible light irradiation showed that the heterostructures are very efficient photocatalysts in mild basic medium. Scavenger test studies confirmed that the photogenerated holes and superoxide radicals (O-2(center dot-)) are the main active species responsible for RhB degradation. Comparison of photoluminescence (PL) intensity suggested that an inhibited charge recombination is crucial for the degradation process over these photocatalysts. Moreover, relative positioning of the valence and conduction band edges of the semiconductors, O-2/O-2(center dot-) and (OH)-O-center dot/H2O redox potentials and HOMO-LUMO levels of RhB appear to be responsible for the hole-specificity of degradation. Photocatalytic recycling experiments indicated the high stability of the catalysts in the reaction medium without any significant loss of activity. This study hence concludes that the heterojunction constructed between Cd(OH)(2) and BiOBr interfaces play a crucial role in influencing the charge carrier dynamics and subsequent photocatalytic activity.

Single-step, size-controlled synthesis of colloidal silver nanoparticles stabilized by octadecylamine

A single step process for the synthesis of size-controlled silver nanoparticles has been developed using a bifunctional molecule, octadecylamine (ODA). Octadecylamine complexes to Ag+ ions electrostatically, reduce them, and subsequently stabilizes the nanoparticles thus formed. Hence, octadecylamine simultaneously functions as both a reducing and a stabilizing agent. The amine-capped nanoparticles can be obtained in the form of dry powder, which is readily redispersible in aqueous and organic solvents. The particle size, and the nucleation and growth kinetics of silver nanoparticles could be tuned by varying the molar ratio of ODA to AgNO3. The UV-vis spectra of nanoparticles prepared with different concentrations of ODA displayed the well-defined plasmon band with maximum absorption around 425 nm. The formation of silver metallic nanoparticles was confirmed by their XRD pattern. The binding of ODA molecule on the surface of silver has been studied by FT-IR and NMR spectroscopy. The formation of well-dispersed spherical Ag nanoparticles has been confirmed by TEM analysis. The particle size and distribution are found to be dependent on the molar concentration of the amine molecule. Open aperture z-scans have been performed to measure the nonlinearity of Ag nanoparticles. (C) 2015 Published by Elsevier B.V.

Use of Sr isotopes as a tool to decipher the soil weathering processes in a tropical river catchment, southwestern India

River water composition (major ion and Sr-87/Sr-86 ratio) was monitored on a monthly basis over a period of three years from a mountainous river (Nethravati River) of southwestern India. The total dissolved solid (TDS) concentration is relatively low (46 mg L-1) with silica being the dominant contributor. The basin is characterised by lower dissolved Sr concentration (avg. 150 nmol L-1), with radiogenic Sr-87/Sr-86 isotopic ratios (avg. 0.72041 at outlet). The composition of Sr and Sr-87/Sr-86 and their correlation with silicate derived cations in the river basin reveal that their dominant source is from the radiogenic silicate rock minerals. Their composition in the stream is controlled by a combination of physical and chemical weathering occurring in the basin. The molar ratio of SiO2/Ca and Sr-87/Sr-86 isotopic ratio show strong seasonal variation in the river water, i.e., low SiO2/Ca ratio with radiogenic isotopes during non-monsoon and higher SiO2/Ca with less radiogenic isotopes during monsoon season. Whereas, the seasonal variation of Rb/Sr ratio in the stream water is not significant suggesting that change in the mineral phase being involved in the weathering reaction could be unlikely for the observed molar SiO2/Ca and Sr-87/Sr-86 isotope variation in river water. Therefore, the shift in the stream water chemical composition could be attributed to contribution of ground water which is in contact with the bedrock (weathering front) during non-monsoon and weathering of secondary soil minerals in the regolith layer during monsoon. The secondary soil mineral weathering leads to limited silicate cation and enhanced silica fluxes in the Nethravati river basin. (C) 2015 Elsevier Ltd. All rights reserved.

On the Structural Stability of Melt Spun Ribbons of Fe95-x Zr (x) B4Cu1 (x=7 and 9) Alloys and Correlation with Their Magnetic Properties

Melt spun ribbons of Fe95-x Zr (x) B4Cu1 with x = 7 (Z7B4) and 9 (Z9B4) alloys have been prepared, and their structure and magnetic properties have been evaluated using XRD, DSC, TEM, VSM, and Mossbauer spectroscopy. The glass forming ability (GFA) of both alloys has been calculated theoretically using thermodynamical parameters, and Z9B4 alloy is found to possess higher GFA than that of Z7B4 alloy which is validated by XRD results. On annealing, the amorphous Z7B4 ribbon crystallizes into nanocrystalline alpha-Fe, whereas amorphous Z9B4 ribbon shows two-stage crystallization process, first partially to bcc solid solution which is then transformed to nanocrystalline alpha-Fe and Fe2Zr phases exhibiting bimodal distribution. A detailed phase analysis using Mossbauer spectroscopy through hyperfine field distribution of phases has been carried out to understand the crystallization behavior of Z7B4 and Z9B4 alloy ribbons. In order to understand the phase transformation behavior of Z7B4 and Z9B4 ribbons, molar Gibbs free energies of amorphous, alpha-Fe, and Fe2Zr phases have been evaluated. It is found that in case of Z7B4, alpha-Fe is always a stable phase, whereas Fe2Zr is stable at higher temperature for Z9B4. (C) The Minerals, Metals & Materials Society and ASM International 2015

Effect of applied pressure on densification of monolithic ZrCx ceramic by reactive hot pressing

The effect of applied pressure on reactive hot pressing (RHP) of zirconium (Zr):graphite (C) in molar ratios of 1:0.5, 1:0.67, 1:0.8, and 1:1 was studied at 1200 degrees C for 60 min. The relative density achievable increased with increasing pressure and ranged from 99% at 4 MPa for ZrC0.5 to 93% for stoichiometric ZrC at 100 MPa. The diminishing influence of pressure on the final density with increasing stoichiometry is attributed to two causes: the decreasing initial volume fraction of the plastically deforming Zr metal which leads to the earlier formation of a contiguous, stress shielding carbide skeleton and the larger molar volume shrinkage during reaction which leads to pore formation in the final stages. A numerical model of the creep densification of a dynamically evolving microstructure predicts densities that are consistent with observations and confirm that the availability of a soft metal is primarily responsible for the achievement of such elevated densification during RHP. The ability to densify nonstoichiometric compositions like ZrC0.5 at pressures as low as 4 MPa offers an alternate route to fabricating dense nonstoichiometric carbides.

The interaction between poly(vinylpyrrolidone) and reversed micelles of water/AOT/n-heptane

The interactions between poly(vinylpyrrolidone) (PVP) and the reversed micelles composed of water, AOT, and n-heptane are investigated with the aid of phase diagram, measurements of conductivity and viscosity, Fourier transform infrared (FTIR) spectrum, and dynamic light scattering (DLS). The phase diagrams of water/AOT/heptane in the presence of and absence of PVP are given. The conductivity of the water/AOT/heptane reversed micelle without PVP initially increases and then decreases with the increase of water content, ω0 (the molar ratio of water to AOT), while the plots of conductivity (K) versus ω0 of the reversed micelle in the presence of PVP depend on the PVP concentrations. The plot of K versus ω0 with 2.0%wt PVP is similar to that without PVP. Only the ω0,max (the water content that the maximum conductivity corresponds to) is larger than that without PVP. Nevertheless, the conductivity of the reversed micelle containing more than 4%wt PVP always rises with the increase of the water content in the measured range. The DLS results indicate that the hydrodynamic radius (Rh) in the presence and absence of PVP rises with the increase of ω0. The plots with PVP and without PVP have almost the same value when ω0<17; and after that, it quickly increases with the increase of ω0. It is interesting to find that there is almost no effect of the PVP concentration on the viscosity and Rh of the reversed micelle at ω0 = 15. The FTIR results suggest that the contents of SO3--bound water and Na+-bound water both decrease with PVP added, while the content of the bulky-like water increases. However, the trapped water in the hydrophobic chain of the surfactant is nearly unaffected by PVP. It is also found from the FTIR that the carbonyl group stretching vibration of AOT is fitted into two sub-peaks, which center at 1740 and 1729 cm-1, corresponding to the trans and cis conformations of AOT, respectively.

Preparation And Optical Properties Of Cdte/Cdo Center Dot Nh(2)O Core/Shell Nano-Composites In Aqueous Solution

The deposition of CdO center dot nH(2)O On CdTe nanoparticles was studied in an aqueous phase. The CdTe nanocrystals (NCs) were prepared in aqueous solution through the reaction between Cd2+ and NaHTe in the presence of thioglycolic acid as a stabilizer. The molar ratio of the Cd2+ to Te2- in the precursory solution played an important role in the photoluminescence of the ultimate CdTe NCs. The strongest photoluminescence was obtained under 4.0 of [Cd2+]/[Te2-] at pH similar to 8.2. With the optimum dosage of Cd(II) hydrous oxide deposited on the CdTe NCs, the photoluminescence was enhanced greatly. The photoluminescence of these nanocomposites was kept constant in the pH range of 8.0-10.0, but dramatically decreased with an obvious blue-shifted peak while the pH was below 8.0. In addition, the photochemical oxidation of CdTe NCs with cadmium hydrous oxide deposition was markedly inhibited.