Molecular precursor mediated selective synthesis of phase pure cubic InSe and hexagonal In2Se3 nanostructures: new anode materials for Li-ion batteries.

Indium selenides (InSe and In2Se3) have earned a special place among the 2D layered metal chalcogenides owing to their nontoxic nature and favourable carrier mobility. Additionally, they are also being projected as next generation battery anodes with high theoretical lithium-ion storage capacities. While the development of indium selenide-based batteries is still in its embryonic stage, a simple and easily scalable synthetic pathway to access these materials is highly desirable for energy storage applications. This study reports a controlled synthetic route to nanometric cubic InSe and hexagonal In2Se3 materials through proper choice of coordinating solvents from a structurally characterized air and moisture stable single source molecular precursor: tris(4,6-dimethyl-2-pyrimidylselenolato)indium(III). The crystal structure, phase purity, composition, morphology and band gap of the nanomaterials were thoroughly evaluated by pXRD, energy dispersive X-ray spectroscopy (EDS), electron microscopy (SEM and TEM), and diffuse reflectance spectroscopy (DRS), respectively. The pristine InSe and In2Se3 nanostructures have been employed as anode materials in lithium-ion batteries (LIBs). Both the cells deliver reasonably high initial discharge capacities with a cyclability of 200 and 620 cycles for cubic InSe and hexagonal In2Se3 respectively with ∼100% coulombic efficiency.

Molecular precursor-mediated facile synthesis of phase pure metal-rich digenite (Cu1.8S) nanocrystals: an efficient anode for lithium-ion batteries.

Copper sulfides have gained significant attention as alternative electrodes for rechargeable batteries. A simple and easily scalable synthetic pathway to access these materials is highly desirable. This paper describes the facile synthesis of metal-rich digenite Cu1.8S nanocrystals from a structurally characterized new single-source molecular precursor in various high boiling solvents of varied polarity. The as-prepared nanostructures were thoroughly characterized by PXRD, Raman spectroscopy, EDS, XPS, electron microscopy techniques and diffuse reflectance spectroscopy to understand the crystal structure, phase purity, elemental composition, morphology and band gap. It was found that the reaction solvent has a profound role on their crystallite size, morphology and band gap, however the crystal structure and phase purity remained unaffected. Pristine Cu1.8S nanostructures have been employed as an anode material in lithium-ion batteries (LIBs). The cell delivers a high initial charge capacity of ∼462 mA h g-1 and retains a capacity of 240 mA h g-1 even after 300 cycles at 0.1 A g-1. DFT calculations revealed that multi-size polyhedron layers in the direction perpendicular to the two Li movement channels aid in the sustainable uptake of Li atoms with controlled volume expansion. The structure-mediated flexibility of the metal-rich Cu1.8S lattice during lithiation permits high cyclability with reasonable retention of capacity.

Dimethyltin(IV)-4,6-dimethyl-2-pyridylselenolate: an efficient single source precursor for the preparation of SnSe nanosheets as anode material for lithium ion batteries.

The air stable tin(IV) complex [Me2Sn{2-SeC5H2(Me-4,6)2N}2] has been synthesized, characterized by NMR, elemental analysis, and single crystal XRD, and employed as a single source molecular precursor (SSP) for the facile synthesis of orthorhombic SnSe nanosheets. The crystal structure, phase purity, morphology and band gap of the nanosheets were investigated by pXRD, EDS, electron microscopy and diffuse reflectance spectroscopy techniques, respectively. It was found that the preferential orientation of planes and the morphology of the nanosheets rely upon the reaction conditions. The band gaps of the nanosheets were blue shifted with respect to the bulk band gap of the material. The synthesized SnSe nanosheets have been employed as an anode material in lithium ion batteries (LIBs). The material exhibits an initial specific capacity of 1134 mA h g-1 at a current density of 50 mA g-1 and was found to retain a capacity of 380 mA h g-1 even after 70 cycles with 100% efficiency.

Di-tert-butyltin(IV) 2-pyridyl and 4,6-dimethyl-2-pyrimidyl thiolates: versatile single source precursors for the preparation of SnS nanoplatelets as anode material for lithium ion batteries.

New air and moisture stable di-tert-butyltin complexes derived from 2-mercaptopyridine (HSpy), [tBu2Sn(Spy)2], [tBu2Sn(Cl)(Spy)] and 4,6-dimethyl-2-mercaptopyrimidine (HSpymMe2) [tBu2Sn(Cl)(SpymMe2)], have been prepared and utilized as single-source molecular precursors for the preparation of orthorhombic SnS nanoplatelets by a hot injection method and thin films by aerosol assisted chemical vapour deposition (AACVD). The complexes were characterized by NMR (1H, 13C, 119Sn) and elemental analysis and their structures were unambiguously established by the single crystal X-ray diffraction technique. Thermolysis of these complexes in oleylamine (OAm) produced SnS nanoplatelets. The morphologies, elemental compositions, phase purity and crystal structures of the resulting Oam-capped nanoplatelets were determined by electron microscopy (SEM, TEM), energy dispersive X-ray spectroscopy (EDS) and pXRD, while the band gaps of the nanoplatelets were evaluated by diffuse reflectance spectroscopy (DRS) and were blue shifted relative to the bulk material. The morphology and preferential growth of the nanoplatelets were found to be significantly altered by the nature of the molecular precursor employed. The synthesized SnS nanoplatelets were evaluated for their performance as anode material for lithium ion batteries (LIBs). A cell comprised of an SnS electrode could be cycled for 50 cycles. The rate capability of SnS was investigated at different current densities in the range 0.1 to 0.7 A g-1 which revealed that the initial capacity could be regained.

Optimization of lithium content in LiFePO4 for superior electrochemical performance: the role of impurities.

Carbon coated Li x FePO4 samples with systematically varying Li-content (x = 1, 1.02, 1.05, 1.10) have been synthesized via a sol-gel route. The Li : Fe ratios for the as-synthesized samples is found to vary from ∼0.96 : 1 to 1.16 : 1 as determined by the proton induced gamma emission (PIGE) technique (for Li) and ICP-OES (for Fe). According to Mössbauer spectroscopy, sample Li1.05FePO4 has the highest content (i.e., ∼91.5%) of the actual electroactive phase (viz., crystalline LiFePO4), followed by samples Li1.02FePO4, Li1.1FePO4 and LiFePO4; with the remaining content being primarily Fe-containing impurities, including a conducting FeP phase in samples Li1.02FePO4 and Li1.05FePO4. Electrodes based on sample Li1.05FePO4 show the best electrochemical performance in all aspects, retaining ∼150 mA h g-1 after 100 charge/discharge cycles at C/2, followed by sample Li1.02FePO4 (∼140 mA h g-1), LiFePO4 (∼120 mA h g-1) and Li1.10FePO4 (∼115 mA h g-1). Furthermore, the electrodes based on sample Li1.05FePO4 retain ∼107 mA h g-1 even at a high current density of 5C. Impedance spectra indicate that electrodes based on sample Li1.05FePO4 possess the least charge transfer resistance, plausibly having influence from the compositional aspects. This low charge transfer resistance is partially responsible for the superior electrochemical behavior of that specific composition.

Revealing magnetic ordering and spin-phonon coupling in Y1-x Tb x MnO3 (0.1 ⩽ x ⩽ 0.3) compounds.

The structural and magnetic properties of the Y1-x Tb x MnO3 (0.1 ⩽ x ⩽ 0.3) compounds were investigated. Neutron diffraction patterns for all three samples, recorded at room temperature (RT), were fitted to the nuclear structure confirming the paramagnetic nature of the compounds. At 2.8 K, for the x = 0.1 sample magnetic moments of the Tb3+ ionic as well as Mn3+ ionic were ordered. At 5 K for the x = 0.2 sample only the Mn3+ ionic magnetic moments were ordered. There were six sites for Mn atoms. Three on the z = 0 plane and three on the z = 0.5 plane (where z corresponds to +c axis).The Mn3+ionic moments were confined to the a-b plane with a net magnitude of 2.78(3) µ B, and 2.90(3) µ B for the x = 0.1 and the x = 0.2 samples. The Tb3+ionic moments had a magnitude of 1.36(4) µ B at 2.8 K and were aligned antiferromagnetically along the crystallographic c-axis for the x = 0.1 sample. The low moment in comparison with Mn3+ free ions has been attributed to crystalline electric fields similar to that found in the parent compound YMnO3 and also in another rare earth manganite viz HoMnO3. The x = 0.3 sample was found to be a canonical spin glass. To investigate the role of the above spin ordering in Y1-x Tb x MnO3 in governing the phonon dynamics, temperature dependent Raman measurements were carried out. We observed the deviation of the phonon frequency near 685 cm-1 and its line-width from the expected anharmonic behaviour around magnetic ordering temperature for Tb substituted compounds with x = 0.1 and 0.2. This was attributed to the spin-phonon coupling in these systems. The anomalous behaviour of this phonon mode in the canonical spin glass compound with x = 0.3, indicated that the coupling sustained even in the presence of only local magnetic ordering.

Synthesis, Characterization and Exploration of Multiferroic Properties in Nano-Crystalline Tb1-xYxMnO3 (0 ≤ x ≤ 0.4).

We report the synthesis and electric properties of nano-crystalline Tb1-xYxMnO3 (x = 0, 0.1, 0.2, 0.3 and 0.4) compounds prepared by gel-combustion method. These samples were characterized by a number of techniques including X-ray diffraction (XRD), Raman spectroscopy, specific-heat measurement, neutron diffraction, and magnetic field dependent pyrocurrent measurement. All the samples crystallize in the orthorhombic structure with space group Pnma at room temperature. Anomalies were observed in low temperature specific-heat measurement corresponding to magnetic and electric phase transitions. The magnetic phase transitions occurred at ~35, ~22-28 and ~7 K for all the samples. Signatures of coupling between magnetic and electric order parameters were revealed by pyrocurrent measurements carried out in presence of magnetic fields.

Effect of grain size and microstructure on radiation stability of CeO2: an extensive study.

To investigate the variation in the radiation stability of ceria with microstructure under the electronic excitation regime, ceria samples sintered under different conditions were irradiated with high energy 100 MeV Ag ions. The ceria nanopowders were synthesized and sintered at 800 °C (S800), 1000 °C (S1000) and 1300 °C (S1300), respectively. The samples with widely varying grain size, densities and microstructure were obtained. The pristine and irradiated samples were studied by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). None of the samples amorphized up to the highest fluence of 1 × 10(14) ions per cm(2) employed in this study. XRD and Raman studies showed that the sample with lowest grain size suffered maximum damage while the sample with largest grain size was most stable and showed little change in crystallinity. Raman spectroscopy indicated the enhanced formation of Ce(3+) and related defects in the sample with larger grain size after irradiation. The most intriguing result was the absence of Ce(3+)-related defects in the sample with lowest grain size which actually showed maximum damage upon irradiation. The XPS studies on S800 and S1300 provided concrete evidence for the presence of Ce(3+) and oxygen ion vacancies in S1300. The grain boundaries and grain size dependent stability have been discussed.

Improved magnetic and ferroelectric properties of Sc and Ti codoped multiferroic nano BiFeO3 prepared via sonochemical synthesis.

The room temperature multiferroic properties of bulk BiFeO3 are not exciting enough for its application in devices. Here, we report the sonochemical synthesis of scandium and titanium codoped BiFeO3 nanoparticles which exhibit improved magnetic and ferroelectric properties at room temperature. The nanoparticles have been checked for phase purity and composition using powder X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). The size and morphology of the nanoparticles have been confirmed using scanning electron microscopy (SEM), and both low and high resolution transmission electron microscopy (TEM/HRTEM). The breaking of the spin cycloid due to the smaller size and slight structural distortion caused by the doping has been found to be instrumental for the enhancement of multiferroic properties. The electrical polarization increases significantly in the case of BiFe(0.925)Sc(0.05)Ti(0.025)O3 nanoparticles. A marked reduction in the leakage current was seen compared to undoped BiFeO3. Magnetoelectric coupling was also observed in the BiFe(0.925)Sc(0.05)Ti(0.025)O3 sample. Our results demonstrate that codoping with Sc and Ti ions is an effective way to rectify and enhance the multiferroic nature of BiFeO3.

Statistical mechanics of DNA rupture: theory and simulations.

We study the effects of the shear force on the rupture mechanism on a double stranded DNA. Motivated by recent experiments, we perform the atomistic simulations with explicit solvent to obtain the distributions of extension in hydrogen and covalent bonds below the rupture force. We obtain a significant difference between the atomistic simulations and the existing results in the literature based on the coarse-grained models (theory and simulations). We discuss the possible reasons and improve the coarse-grained model by incorporating the consequences of semi-microscopic details of the nucleotides in its description. The distributions obtained by the modified model (simulations and theoretical) are qualitatively similar to the one obtained using atomistic simulations.

Hybrid multiferroic nanostructure with magnetic-dielectric coupling.

The development of methods to economically synthesize single wire structured multiferroic systems with room temperature spin-charge coupling is expected to be important for building next-generation multifunctional devices with ultralow power consumption. We demonstrate the fabrication of a single nanowire multiferroic system, a new geometry, exhibiting room temperature magnetodielectric coupling. A coaxial nanotube/nanowire heterostructure of barium titanate (BaTiO(3), BTO) and cobalt (Co) has been synthesized using a template-assisted method. Room temperature ferromagnetism and ferroelectricity were exhibited by this coaxial system, indicating the coexistence of more than one ferroic interaction in this composite system.

Synthesis of uniform gold nanoparticles using non-pathogenic bio-control agent: evolution of morphology from nano-spheres to triangular nanoprisms.

Green synthesis of gold nanospheres with uniform diameter and triangular nanoprisms with optically flat surface was carried out using a non-pathogenic bio-control agent Trichoderma asperellum for reduction of HAuCl(4). Kinetics of the reaction was monitored by UV-Vis absorption spectroscopy. No additional capping/complexing agent was used for stabilizing the gold nanoparticles. Evolution of morphology from pseudospherical nanoparticles to triangular nanoprisms was studied by transmission electron microscopy (TEM). It revealed that three or more pseudospheres fused to form nanoprisms of different shapes and sizes. Slow rate of reduction of HAuCl(4) by constituents of cell-free fungal extract was instrumental in producing such exotic morphologies. Isolation of gold nanotriangles from the reacting masses was achieved by differential centrifugation.

Rare examples of fluoride-based multiferroic materials in Mn-substituted BaMgF4 systems: experimental and theoretical studies.

A series of Mn-substituted BaMgF(4) samples have been synthesized by a hydrothermal route. X-ray diffraction study reveals that the products are monophasic in nature. Scanning electron microscopy (SEM) and energy-dispersive spectrometry (EDS) studies were carried out to investigate the morphology and stoichiometry for these compounds. X-ray photoelectron spectroscoy (XPS) and electron spin resonance (ESR) studies were done to confirm the oxidation state of dopant ion. Room temperature ferromagnetism was observed on Mn substitution at the Mg site in BaMgF(4) samples. The saturation magnetization increases initially, shows a peaking effect, and then decreases with further increase in Mn concentration in BaMg(1-x)Mn(x)F(4) (0.0 ≤ x ≤ 0.15). However, ferroelectricity was found to decrease with an increase in Mn concentration in the series of investigated BaMg(1-x)Mn(x)F(4) (0.0 ≤ x ≤ 0.15) samples. First-principle calculations, using the projector augmented wave potentials on Mn-substituted BaMgF(4), confirmed the decrease in magnetic moment with an increase in Mn content beyond certain concentration. These samples exhibit very weak magnetocapacitive coupling, which can be attributed to the very small magnetic signal observed in these samples.

Crucial role of the reaction conditions in isolating several metastable phases in a Gd-Ce-Zr-O system.

A series of samples with composition Gd(2-y)Ce(y)Zr(2)O(7) (0.0 ≤ y ≤ 2.0) were prepared by the gel combustion method followed by high-temperature reduction. The details of the structural variations as a function of the composition, temperature, and oxygen stoichiometry have been investigated by X-ray diffraction (XRD), high-temperature XRD (HT-XRD), and thermogravimetry. A complete solubility of Gd(3+) in Ce(2)Zr(2)O(7) and Ce(2)Zr(2)O(8) could be achieved by this adaptive preparative method. Analysis of the XRD data revealed a sequential variation of the structural features with oxygen stoichiometry as well as Gd(3+) contents in these compositions. The variation in the unit cell parameter along the compositions has a strong influence on the oxygen uptake behavior in the Gd(2-y)Ce(y)Zr(2)O(7) system, as observed from the thermogravimetric and HT-XRD studies. The preparation and stability of various metastable phases in Gd-Ce-Zr-O have been addressed in detail. The details of the study will be useful for the design and application of a potential redox catalyst and an oxygen storage capacitor.

Green synthesis of highly stabilized nanocrystalline silver particles by a non-pathogenic and agriculturally important fungus T. asperellum.

A controlled and up-scalable biosynthetic route to nanocrystalline silver particles with well-defined morphology using cell-free aqueous filtrate of a non-pathogenic and commercially viable biocontrol agent Trichoderma asperellum is being reported for the first time. A transparent solution of the cell-free filtrate of Trichoderma asperellum containing 1 mM AgNO(3) turns progressively dark brown within 5 d of incubation at 25 °C. The kinetics of the reaction was studied using UV-vis spectroscopy. An intense surface plasmon resonance band at ∼410 nm in the UV-vis spectrum clearly reveals the formation of silver nanoparticles. The size of the silver particles using TEM and XRD studies is found to be in the range 13-18 nm. These nanoparticles are found to be highly stable and even after prolonged storage for over 6 months they do not show significant aggregation. A plausible mechanism behind the formation of silver nanoparticles and their stabilization via capping has been investigated using FTIR and surface-enhanced resonance Raman spectroscopy.