Thickness dependence of wavenumbers and optical-activity selection rule of zone-center phonons in two-dimensional gallium sulfide metal monochalcogenide.

Gallium sulfide (GaS) stands out as a versatile nonlinear optical material for green-blue optoelectronic and photocatalytic nano-devices. In addition, the in-plane breaking strain and mechanical strength of layered GaS make it a promising candidate for next-generation flexible nanodevices. The fast and reliable assessment of the number of layers, without sample loss, is key for these applications. Here we unveil the influence of dimensionality in the structural, mechanical, and vibrational properties of GaS by applying density-functional theory-based quantum-simulations and group-theory analysis. We find its intralayer structure and interlayer distances are essentially independent of the number of layers, in agreement with the van der Waals forces as dominant interlayer interactions. The translational symmetry breaking along the stacking direction results in different structural symmetries for monolayers, N-odd layers, N-even layers, and bulk geometries. Its force constants against rigid-layer shear, KLSM = 1.35 × 1019 N m-3, and breathing, KLBM = 5.00 × 1019 N m-3, displacements remain the same from bulk to bilayer structures. The related stiffness coefficients in bulk are C44 = 10.2 GPa and C33 = 37.7 GPa, respectively. This insight into GaS interlayer interactions and elastic coefficients reveals it as a promising lubricant for nano-mechanic applications and it is easy to cleave for thickness engineering, even in comparison with layered graphite, MoS2 and other transition metal dichalcogenides and group-IIIA metal monochalcogenides. We present the GaS Raman and infrared spectra dependence on the layer number as strategies for sample thickness characterization and derive formulas for distinguishing the number of layers in both high and low-frequency regimes. In addition, our analysis of their optical-activity selection rules and polarization dependencies is applicable to isostructural group-IIIA metal monochalcogenides with 2H-layer stacking, such as gallium/indium sulphide/selenide. These results contribute to rapid and non-destructive characterization of the material's structure, which is of paramount importance for the manufacturing of devices and the utilization of its diverse properties.

Room-temperature highly sensitive and selective NH3gas sensor using vertically aligned WS2nanosheets.

Here, we report the room temperature (35 °C) NH3gas sensor device made from WS2nanosheets obtained via a facile and low-cost probe sonication method. The gas-sensing properties of devices made from these nanosheets were examined for various analytes such as ammonia, ethanol, methanol, formaldehyde, acetone, chloroform, and benzene. The fabricated gas sensor is selective towards NH3and exhibits excellent sensitivity, faster response, and recovery time in comparison to previously reported values. The device can detect NH3down to 5 ppm, much below the maximum allowed workspace NH3level (20 ppm), and have a sensing response of the order of 112% with a response and recovery time of 54 s and 66 s, respectively. On the other hand, a sensor made from nanostructures has a bit longer recovery time than a device made from nanosheets. This was attributed to the fact that NH3molecules adsorbed on the surface site and those trapped in between WS2layers may have different adsorption energies . In the latter case, desorption becomes difficult and may give rise to slower recovery as noticed. Further, stiffened Raman modes upon exposure to NH3reveal strong electron-phonon interaction between NH3and the WS2channel. The present work highlights the potential use of scaled two-dimensional nanosheets in sensing devices and particularly when used with inter-digitized electrodes, may offer enhanced performance.

Functional Monochalcogenides: Raman Evidence Linking Properties, Structure, and Metavalent Bonding.

Pressure- and temperature-dependent Raman scattering in GeSe, SnSe, and GeTe for pressures beyond 50 GPa and for temperatures ranging from 78 to 800 K allow us to identify structural and electronic phase transitions, similarities between GeSe and SnSe, and differences with GeTe. Calculations help to deduce the propensity of GeTe for defect formation and the doping that results from it, which gives rise to strong Raman damping beyond anomalous anharmonicity. These properties are related to the underlying chemical bonding and consistent with a recent classification of bonding in several chalcogenide materials that puts GeTe in a separate class of "incipient" metals.

Pressure-Induced Phase Transitions in Germanium Telluride: Raman Signatures of Anharmonicity and Oxidation.

Pressure-induced phase transitions in GeTe, a prototype phase change material, have been studied to date with diffraction which is not sensitive to anharmonicity-induced dynamical effects. GeTe is also prone to surface oxidation which may compromise surface sensitive measurements. These factors could be responsible for the lack of clarity about the phases and transitions intervening in the phase diagram of GeTe. We have used high-pressure Raman scattering and ab initio pseudopotential density functional calculations to unambiguously establish the high-pressure phase diagram and identify three phases up to 57 GPa, a low-pressure rhombohedral phase, an intermediate pressure cubic phase, and a high-pressure orthorhombic phase. We detect substantial broadening and softening of Raman modes at low pressure and identify the transition regions and possible intermediate phases.

Graphene quantum dots as enhanced plant growth regulators: effects on coriander and garlic plants.

BACKGROUND: We report investigations on the use of graphene quantum dots for growth enhancement in coriander (Coriandrum sativam L.) and garlic (Allium sativum) plants. The as-received seeds of coriander and garlic were treated with 0.2 mg mL(-1) of graphene quantum dots for 3 h before planting. RESULTS: Graphene quantum dots enhanced the growth rate in coriander and garlic plants, including leaves, roots, shoots, flowers and fruits, when the seeds were treated with graphene quantum dots. CONCLUSION: Our investigations open up the opportunity to use graphene quantum dots as plant growth regulators that can be used in a variety of other food plants for high yield.

Thermal expansion, anharmonicity and temperature-dependent Raman spectra of single- and few-layer MoSe2 and WSe2.

We report the temperature-dependent Raman spectra of single- and few-layer MoSe2 and WSe2 in the range 77-700 K. We observed linear variation in the peak positions and widths of the bands arising from contributions of anharmonicity and thermal expansion. After characterization using atomic force microscopy and high-resolution transmission electron microscopy, the temperature coefficients of the Raman modes were determined. Interestingly, the temperature coefficient of the A(2)(2u) mode is larger than that of the A(1g) mode, the latter being much smaller than the corresponding temperature coefficients of the same mode in single-layer MoS2 and of the G band of graphene. The temperature coefficients of the two modes in single-layer MoSe2 are larger than those of the same modes in single-layer WSe2. We have estimated thermal expansion coefficients and temperature dependence of the vibrational frequencies of MoS2 and MoSe2 within a quasi-harmonic approximation, with inputs from first-principles calculations based on density functional theory. We show that the contrasting temperature dependence of the Raman-active mode A(1g) in MoS2 and MoSe2 arises essentially from the difference in their strain-phonon coupling.

1D and 2D Boron Nitride Nano Structures: A Critical Analysis for Emerging Applications in the Field of Nanocomposites.

Boron nitride (BN) with its 1D and 2D nano derivatives have gained immense popularity in both the field of research and applications. These nano derivatives have proved to be one of the most promising fillers which can be incorporated in polymers to form nanocomposites with excellent properties. These materials have been around for 25 years whereas significant research has been done in this field for only the past decade. There are many interesting properties which are imparted to the nanocomposites wherein thermal stability, large energy band gap, resistance to oxidation, excellent thermal conductivity, chemical inertness, and exceptional mechanical properties are just a few worthy of mention. Hexagonal boron nitride (h-BN) was selected as the parent material by most researchers reviewed in this paper through which 2D derivative Boron nitride nanosheets (BNNS) and 1D derivative Boron nitride nanotubes (BNNTs) are synthesized. This review will focus on the in-depth properties of h-BN and further will concisely focus on BNNS and BNNTs for their various properties. A detailed discussion of the addition of BNNS and BNNTs into polymers to form nanocomposites, their synthesis, properties, and applications is followed by a summary determining the most suitable synthesizing processes and the materials, keeping in mind the current challenges.

Enhanced sunlight-driven catalysis for hydrogen generation and dye remediation using synergistic p-Co3O4/n-TiO2 nanocomposites.

In this study, p-Co3O4/n-TiO2 nanocomposites were synthesized using different ratios of cobalt and titanium precursors through a hydrothermal method. These nanocomposites demonstrated notable potential in photocatalytic applications for hydrogen production and orange-red dye degradation under sunlight. Various techniques, including XRD, Raman spectroscopy, XPS, FESEM, TEM, and BET analysis, were used to comprehensively characterize their structural, morphological, and optical properties. The nanocomposites exhibited both cubic and tetragonal phases of Co3O4 and TiO2, and their combined effect resulted in a narrowed band gap. Additionally, the presence of Co3O4 induced surface plasmon resonance on the TiO2 surface, effectively impeding electron-hole recombination. The nanocomposites displayed an average particle size of ∼20 to 30 nm with substantial visible light absorption. High crystallinity and well-dispersed nanocomposites were confirmed by XRD and Raman, with BET surface areas ranging between 49 and 106 m2 g-1. Notably, the p-Co3O4/n-TiO2 nanocomposite showed superior photocatalytic activity, achieving a maximum hydrogen generation rate of 1120 µmol h-1 g-1 and an 83% degradation efficiency of the orange-red dye within 6 minutes under sunlight. This study emphasizes the enhanced performance of the p-Co3O4/n-TiO2 nanocomposite, indicating its potential in photocatalytic applications, conforming to a pseudo-first-order kinetics model.

Solution-based electrostatic self-assembly route for obtaining graphene-transition metal dichalcogenide heterostructures.

Heterostructures of 2D materials have provided splendid insights into fundamental phenomena and are also promising for numerous applications. However, the protocols for obtaining them remain highly specific and lack scalability. Herein, the demonstrated protocol employs surfactant-assisted exfoliation and centrifugation-based size-selection of nanosheets for synthesizing heterostructures through electrostatic self-assembly.

Surface modification of a biomass-derived self-supported carbon nano network as an emerging platform for advanced field emitter devices and supercapacitor applications.

Herein, a self-supported carbon network is designed through the sole pyrolysis of Carica papaya seeds (biomass) without any activation agent, demonstrating their field emission and supercapacitor applications. The pyrolysis of seeds in an argon atmosphere leads to the formation of interconnected, rod-like structures. Furthermore, the hydrofluoric acid treatment not only removed impurities, but also resulted in the formation of CaF2 nanocrystals with the addition of F-doping. From the field emission studies, the turn-on field values defined at an emission current density of ∼10 µA cm-2 were found to be ∼2.16 and 1.21 V µm-1 for the as-prepared carbon and F-doped carbon, respectively. Notably, F-doped carbon exhibits a high emission current density of ∼9.49 mA cm-2 and has been drawn at an applied electric field of ∼2.29 V µm-1. Supercapacitor studies were carried out to demonstrate the multi-functionality of the prepared materials. The F-doped carbon electrode material exhibits the highest specific capacitance of 234 F g-1 at 0.5 A g-1. To demonstrate the actual supercapacitor application, the HFC//HFC symmetric coin cell supercapacitor device was assembled. The overall multifunctional applicability of the fabricated hybrid structures provides a futuristic approach to field emission and energy storage applications.

Synthesis and characterization of micro-/nano-α-Fe2O3 for photocatalytic dye degradation.

Photocatalytic activity using micro-/nano-α-Fe2O3 on a large scale was carried out using a sol-gel autocombustion method. A degradation time of 60 min was noted for 50 mg of the catalyst. Post characterization, this catalyst system showed a degradation of about 53% (rate = 2.60 × 10-3 min-1) and 17% (rate = 1.38 × 10-2 min-1) under sunlight and up to 45% (rate = 1.13 × 10-3 min-1) and 7% (rate = 1.20 × 10-2 min-1) under a 400 W UV lamp for rhodamine 6G (R6G) and crystal violet (CV), respectively. Sunlight has a broad spectrum of light; it greatly accelerates the degradation process and creates ideal conditions for the reaction to occur. The rate of photocatalytic dye degradation of α-Fe2O3 without Fenton's reagent was found to be 7.84 × 10-3 min-1 in the presence of external air provided (in the photocatalytic setup) through a bubbler and 3.23 × 10-3 min-1 in the absence of the bubbler.

Enhanced field-emission behavior of layered MoS2 sheets.

Field emission studies are reported for the first time on layered MoS2 sheets at the base pressure of ∼1 × 10⁻8 mbar. The turn-on field required to draw a field emission current density of 10 µA/cm² is found to be 3.5 V/µm for MoS2 sheets. The turn-on values are found to be significantly lower than the reported MoS2 nanoflowers, graphene, and carbon nanotube-based field emitters due to the high field enhancement factor (∼1138) associated with nanometric sharp edges of MoS2 sheet emitter surface. The emission current-time plots show good stability over a period of 3 h. Owing to the low turn-on field and planar (sheetlike) structure, the MoS2 could be utilized for future vacuum microelectronics/nanoelectronic and flat panel display applications.

MoS2 nanobelts-carbon hybrid material for supercapacitor applications.

The MoS2 nanobelts/Carbon hybrid nanostructure was synthesized by the simple hydrothermal method. The MoS2 nanobelts were distributed in the interlayers of Lemon grass-derived carbon (LG-C), provides the active sites and avoid restacking of the sheets. The structural and morphological characterization of MoS2/LG-C and LG-C were performed by Raman spectroscopy, X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The electrochemical measurements were studied with cyclic voltammetry, the galvanostatic charge-discharge method, and electrochemical impedance spectroscopy. The specific capacitance of MoS2/LG-C and LG-C exhibits 77.5 F g-1 and 30.1 F g-1 at a current density of 0.5 A g-1. The MoS2/LG-C-based supercapacitor provided the maximum power density and energy density of 273.2 W kg-1 and 2.1 Wh kg-1, respectively. Furthermore, the cyclic stability of MoS2/LG-C was tested using charging-discharging up to 3,000 cycles, confirming only a 71.6% capacitance retention at a current density of 3 A g-1. The result showed that MoS2/LG-C is a superior low-cost electrode material that delivered a high electrochemical performance for the next generation of electrochemical energy storage.

Copper(ii) and cobalt(iii) Schiff base complexes with hydroxy anchors as sensitizers in dye-sensitized solar cells (DSSCs).

Two Schiff base complexes of copper(ii) and cobalt(iii) having the formulae [CuL2] (Cu-Sal) and [CoL3] (Co-Sal) (HL = 2-(((2-hydroxyethyl)imino)methyl)phenol) have been synthesized and characterized microanalytically, spectroscopically and in the case of Cu-Sal using single crystal X-ray diffraction technique. The single crystal X-ray analysis reveals a square planar geometry around Cu(ii) satisfied by phenoxide oxygen and imine nitrogen of the L- ligand to generate a six membered chelate ring. The solid state structure of Cu-Sal is satisfied by varied intermolecular non-covalent interactions. The nature of these interactions has been addressed with the aid of Hirshfeld surface analysis. Both compounds have been used as sensitizers in TiO2 based dye sensitized solar cells (DSSCs) and the DSSC experiments revealed that Co-Sal offers better photovoltaic performance in comparison to Cu-Sal. The Co-Sal exhibited a J sc of 9.75 mA cm-2 with a V oc of -0.648 V, incident photon to current conversion efficiency (IPCE) of 57% and η of 3.84%. The relatively better photovoltaic performance of Co-Sal could be attributed to better light absorption and dye loading than that of Cu-Sal.

Temperature effects on the Raman spectra of graphenes: dependence on the number of layers and doping.

Temperature effects on the various features in the Raman spectra of several graphene samples and graphene nanoribbons have been investigated over the temperature range 77-573 K. The temperature coefficient of the G and 2D band frequencies are found to depend on the number of layers, the former decreasing with the increase in the number of layers. The number of layers also affects the temperature coefficients of the FWHMs of these bands. Doping of graphene affects these Raman features significantly. The defect-related bands D and D(') bands are not sensitive to the number of layers or doping. We can understand the observed temperature effects on the basis of electron-phonon coupling, thermal expansion and anharmonic phonon-phonon interactions.

Enhanced energy storage performance and theoretical studies of 3D cuboidal manganese diselenides embedded with multiwalled carbon nanotubes.

The burst of energy produced from the sustainable energy sources need to be harnessed by energy storage systems. Development of novel and advanced energy storage devices such as supercapacitors discover an enormous future ahead. Recently, hybrid supercapacitors (electric double layer capacitor (EDLC) and pseudocapacitors) trend to be used as energy storage interfaces for their improved efficacy in energy density without altering the power density. In the ongoing workplan, transition metal selenides MnSe2 and its hybrid with multiwalled carbon nanotubes (MWCNTs) are synthesized by a simplistic hydrothermal protocol. Certainly, cubic phases of MnSe2-MWCNT(MS/CNT) manifested superior electrochemical performance in both symmetric and asymmetric full cell configurations in contrast to prestine MnSe2(MS). The asymmetric MS/CNT cell achieved an excellent charge storage capability with an high energy density of 39.45 Wh kg-1 at a power density of 2.25 kW kg-1 maintaining an energy density of 14.5 Wh kg-1 at a high power density of 4.5 kWh kg-1 and also revealed long term stability over 5000 consecutive charge/discharge cycles (capacitance retention of 95.2%). Furthermore, the preferable growth along (200) direction in the presence of MWCNTs favoured in enriching the supercapacitive property of MS. The quantum capacitance of MnSe2surfaces and MS/CNT heterostructure has been estimated using density functional theory simulation to confirm the experimental outcomes. Theoretical investigation simultaneously exposed the contribution of (200) plane of MnSe2 and MWCNTs cultured in enhanced DOS (density of states) near the Fermi level that remarkably promoted the energy storage efficiency of MS/CNT.

MoS2 and CdMoS4 nanostructure-based UV light photodetectors.

We have developed MoS2 nanosheets and CdMoS4 hierarchical nanostructures based on a UV light photodetector. The surface morphologies of the as-prepared samples were investigated via field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The performance parameters for the present photodetectors are investigated under the illumination of UV light having a wavelength of ∼385 nm. Upon the illumination of UV light, the CdMoS4-based photodetector device showed a better response to UV light compared to the MoS2 device in terms of photoresponsivity, response time (∼72 s) and recovery time (∼94 s). Our results reveal that CdMoS4 hierarchical nanostructures are practical for enhancing the device performance.

Highly sensitive and flexible pressure sensor based on two-dimensional MoSe2 nanosheets for online wrist pulse monitoring.

The advancement of portable and flexible electronics that is integrated with multiple sensing functions has increasingly drawn considerable interest. The fabricated sensors would have the ability to sense multiple deformations like pressing, twisting and trivial vibrations such as pulses of wrist vibrations to mimic human skin. Presently, we implemented an easy, cost-effective and optimized fabrication technique for production of pressure sensors based on MoSe2 nanosheets coated on cellulose paper. The present sensor exhibits an incorporation of large pressure sensitivity of 18.42 kPa-1 in pressure range 0.001-0.5 kPa, 7.28 kPa-1 in pressure range 1-35 kPa and 2.63 kPa-1 in pressure range 40-100 kPa, working in broad pressure range (from 0.001 to 100 kPa) and long-term stability up to 200 deformation cycles at 2 kPa. The sensor showed excellent response towards the detection of vibrations of machines including cellular phone, compressor, etc. Besides, the sensor shows excellent environmental stability and exhibits immune piezo-resistive response to temperature variation.

A study of the synthetic methods and properties of graphenes.

Graphenes with varying number of layers can be synthesized by using different strategies. Thus, single-layer graphene is prepared by micromechanical cleavage, reduction of single-layer graphene oxide, chemical vapor deposition and other methods. Few-layer graphenes are synthesized by conversion of nanodiamond, arc discharge of graphite and other methods. In this article, we briefly overview the various synthetic methods and the surface, magnetic and electrical properties of the produced graphenes. Few-layer graphenes exhibit ferromagnetic features along with antiferromagnetic properties, independent of the method of preparation. Aside from the data on electrical conductivity of graphenes and graphene-polymer composites, we also present the field-effect transistor characteristics of graphenes. Only single-layer reduced graphene oxide exhibits ambipolar properties. The interaction of electron donor and acceptor molecules with few-layer graphene samples is examined in detail.

TiO2 nanoflowers based humidity sensor and cytotoxic activity.

We have systematically investigated the humidity sensing performance and cytotoxic activity of TiO2 nanoflowers synthesized by hydrothermal method. Our result reveals that TiO2 nanoflower based sensor devices show good performance at room temperature with a maximum sensitivity of ∼815% along with a response time of ∼143 s and a recovery time of ∼33 s. Our findings also evaluate the cytotoxic effect of TiO2 nanoflowers on human HepG2 cell lines. The cells are cultured in DMEM medium with varying concentrations of TiO2 nanoflowers for 24, 48 and 72 hours respectively. The results indicate that TiO2 nanoflower doses time dependently suppress the proliferation of HepG2 cell lines.