Engineering of Solar Energy Harvesting Tb3+-Ion-Doped CdS Quantum Dot Glasses for Photodissociation of Hydrogen Sulfide.

The photocatalytic properties of CdS quantum dots (Q-dots) and Tb3+-doped CdS Q-dots dispersed in a borosilicate glass matrix were investigated for the photodissociation of hydrogen sulfide (H2S) into hydrogen (H2) gas and elemental sulfur (S). The Q-dot-containing glass samples were fabricated using the conventional melt-quench method and isothermal annealing between 550 and 600 °C for 6 h for controlling the growth of CdS and Tb3+-ion-doped CdS Q-dots. The structure, electronic band gap, and spectroscopic properties of the Q-dots formed in the glass matrix after annealing were analyzed using Raman and UV-visible spectroscopies, X-ray powder diffraction, and transmission electron microscopy. With increasing annealing temperature, the average size range of the Q-dots increased, corresponding to the decrease of electronic band gap from 3.32 to 2.24 eV. For developing the model for photocatalytic energy exchange, the excited state lifetime and photoluminescence emission were investigated by exciting the CdS and Tb3+-doped CdS quantum states with a 450 nm source. The results from the photoluminescence and lifetime demonstrated that the Tb3+-CdS photodissociation energy exchange is more efficient from the excited Q-dot states compared to the CdS Q-dot glasses. Under natural sunlight, the hydrogen production experiment was conducted, and an increase of 26.2% in hydrogen evolution rate was observed from 0.02 wt % Tb3+-doped CdS (3867 µmol/h/0.5 g) heat-treated at 550 °C when compared to CdS Q-dot glass with a similar heat treatment temperature (3064 µmol/h/0.5 g). Furthermore, the photodegradation stability of 0.02 wt % Tb3+-CdS was analyzed by reusing the catalyst glass powders four times with little evidence of degradation.

The synthesis and super capacitive characterization of microwave-assisted highly crystalline α-Fe2O3/Fe3O4 nanoheterostructures.

A facile microwave-assisted solvothermal process for the synthesis of narrow-size distributed α-Fe2O3, α-Fe2O3/Fe3O4, and Fe3O4 nanostructures was demonstrated using PVP as a surfactant. During the reaction, the influence of the reaction media, such as the mixture of ethylene glycol and water on the formation of α-Fe2O3, α-Fe2O3/Fe3O4, and Fe3O4 was systematically studied. Interestingly, pure aqueous medicated solvothermal reaction conferred phase pure rhombohedral Fe2O3 (hematite) and linearly upsurging the formation of cubic Fe3O4 (magnetite) with the increasing concentration of EG and further, in pure EG, it deliberated cubic Fe3O4. FESEM and FETEM images of α-Fe2O3/Fe3O4 nano heterostructure clearly showed the nanosized Fe3O4 particles of 4-6 nm decorated onto Fe2O3 nanoparticles. Further, the electrochemical properties of α-Fe2O3, α-Fe2O3/Fe3O4, and Fe3O4 nanoparticles were investigated with galvanostatic charge-discharge and cyclic voltammetry measurements using a 3-electrode system. The findings show that their specific capacitances are linked to the type of iron oxide. More significantly, the α-Fe2O3/Fe3O4 nanoheterostructure exhibited the utmost capacitance of 165 F g-1, which is greater than that of pristine α-Fe2O3 and Fe3O4. Enhancement in the electrochemical performance was found due to the improved charge transfer that occurred at the interface of the nanoheterostructure. The nanoparticles of Fe3O4 deposited on the Fe2O3 increased the active sites, which accelerated the process of adsorption and desorption of ions, thereby enhancing the interface-assisted charge transfer and reducing the internal resistance, which is ultimately responsible for enhanced capacitance. Such heterostructures of nano iron oxide may fulfill the requirements of electrodes in supercapacitors.

Nanostructured gold in ancient Ayurvedic calcined drug 'swarnabhasma'.

BACKGROUND: Swarnabhasma (calcined gold) is a famous ancient Ayurvedic medicine. However, its detail characteristic investigations are very limited. OBJECTIVE: Herein, investigation of swarnabhasma is demonstrated using ancient and ultramodern techniques to understand the physicochemical nature of this drug, and to understand whether the mercury [Parada] used during preparation method marks its presence in swarnabhasma. MATERIALS AND METHODS: The investigated swarnabhasma was prepared by repeated incinerations of Au-Hg-Lemon juice amalgamation and sulphur. The bhasma was tested by all traditional tests of rasashastra. It was characterized by X-ray diffraction (XRD), Field Emission Scanning Electron Microscope (FE-SEM), Field Emission Transmission Electron Microscopy (FE-TEM), Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), Energy Dispersive X-ray Fluorescence (EDXRF), Fourier Transform Infrared Spectroscopy (FTIR), and gravimetric analysis. RESULTS: Traditional tests of rasashastra were complied by the sample. XRD confirms that swarnabhasma consists of principally pure gold at nanoscale. FE-SEM showed agglomerated particles. FE-TEM showed that swarnabhasma contains highly crystalline nanostructured gold comprised with spherical gold nanoparticles of size, 5-20 nm. ICP-AES exhibited absolute absence of Hg and presence of Au, Si, Ag, Al, Ca, Cu, Fe, K, Mg, Mn, Na, P, Sr, Ti, and Zn. EDXRF confirmed the absence of mercury and confirmed the presence of Au, Si, Zr, Nb, S, Cl, K, Ca, Fe, and Ni. FTIR confirmed presence of water molecules adsorbed over surface of bhasma. Gravimetric analysis confirmed presence of 95% gold. CONCLUSION: Nano-structuring of gold enhances the surface area as well as activity. The present investigation shows that the entire process from rasashastra confers the unique nanostructure to gold and same is responsible for its medicinal potential. This nanomedicine is highly stable, which is specified as niruttha and apunarbhava in rasashastra.

Efficient solar light-driven hydrogen generation using an Sn3O4 nanoflake/graphene nanoheterostructure.

Herein, we report Sn3O4 and Sn3O4 nanoflake/graphene for photocatalytic hydrogen generation from H2O and H2S under natural "sunlight" irradiation. The Sn3O4/graphene composites were prepared by a simple hydrothermal method at relatively low temperatures (150 °C). The incorporation of graphene in Sn3O4 exhibits remarkable improvement in solar light absorption, with improved photoinduced charge separation due to formation of the heterostructure. The highest photocatalytic hydrogen production rate for the Sn3O4/graphene nanoheterostructure was observed as 4687 µmol h-1 g-1 from H2O and 7887 µmol h-1 g-1 from H2S under natural sunlight. The observed hydrogen evolution is much higher than that for pure Sn3O4 (5.7 times that from H2O, and 2.2 times from H2S). The improved photocatalytic activity is due to the presence of graphene, which acts as an electron collector and transporter in the heterostructure. More significantly, the Sn3O4 nanoflakes are uniformly and parallel grown on the graphene surface, which accelerates the fast transport of electrons due to the short diffusion distance. Such a unique morphology for the Sn3O4 along with the graphene provides more adsorption sites, which are effective for photocatalytic reactions under solar light. This work suggests an effective strategy towards designing the surfaces of various oxides with graphene nanoheterostructures for high performance of energy-conversion devices.

Unique hierarchical SiO2@ZnIn2S4 marigold flower like nanoheterostructure for solar hydrogen production.

The novel marigold flower like SiO2@ZnIn2S4 nano-heterostructure was fabricated using an in situ hydrothermal method. The nanoheterostructure exhibits hexagonal structure with marigold flower like morphology. The porous marigold flower assembly was constructed using ultrathin nanosheets. Interestingly, the thickness of the nanopetal was observed to be 5-10 nm and tiny SiO2 nanoparticles (5-7 nm) are decorated on the surface of the nanopetals. As the concentration of SiO2 increases the deposition of SiO2 nanoparticles on ZnIn2S4 nanopetals increases in the form of clusters. The optical study revealed that the band gap lies in the visible range of the solar spectrum. Using X-ray photoelectron spectroscopy (XPS), the chemical structure and valence states of the as-synthesized SiO2@ZnIn2S4 nano-heterostructure were confirmed. The photocatalytic activities of the hierarchical SiO2@ZnIn2S4 nano-heterostructure for hydrogen evolution from H2S under natural sunlight have been investigated with regard to the band structure in the visible region. The 0.75% SiO2@ZnIn2S4 showed a higher photocatalytic activity (6730 µmol-1 h-1 g-1) for hydrogen production which is almost double that of pristine ZnIn2S4. Similarly, the hydrogen production from water splitting was observed to be 730 µmol-1 h-1 g-1. The enhanced photocatalytic activity is attributed to the inhibition of charge carrier separation owing to the hierarchical morphology, heterojunction and crystallinity of the SiO2@ZnIn2S4.

Fragmented lignin-assisted synthesis of a hierarchical ZnO nanostructure for ammonia gas sensing.

In the present study, we demonstrated the use of fragmented lignin in the synthesis of a hierarchical-type structure of ZnO nanorods. Lignin was isolated from bagasse by the microwave assisted method and its fragmentation was achieved in alkaline conditions along with hydrogen peroxide. Lignin and fragmented lignin were purified by crystallisation followed by column chromatography and characterized by UV-visible spectroscopy, Frontier infra-red spectroscopy (FTIR), 1H-NMR and high resolution mass spectroscopy (HRMS). Fragmented lignin was utilized as a template for the synthesis of ZnO nanorods, which were characterized by powder XRD, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-DRS for the determination of crystal structure, particle morphology and band gap. XRD of the ZnO samples revealed a hexagonal wurtzite structure. The morphology of ZnO without fragmented lignin showed agglomerated nanoparticles and with fragmented lignin, a self-assembled hierarchical nanostructure due to nanorods of 30 nm diameter and 200-500 nm length was observed. The fragmented lignin showed a pronounced effect on the particle size and morphology of ZnO nanoparticles. We measured the response of the hierarchical ZnO nanostructure (50 ppm) for sensing NH3 in terms of change in voltage across known resistance. We observed the response and recovery upon introduction of the analyte ammonia gas at 175 °C.

Plasmonic Ag decorated CdMoO4 as an efficient photocatalyst for solar hydrogen production.

The synthesis of Ag-nanoparticle-decorated CdMoO4 and its photocatalytic activity towards hydrogen generation under sunlight has been demonstrated. The CdMoO4 samples were synthesized by a simple hydrothermal approach in which Ag nanoparticles were in situ decorated on the surface of CdMoO4. A morphological study showed that 5 nm spherical Ag nanoparticles were homogeneously distributed on the surface of CdMoO4 particles. The UV/DRS spectra show that the band gap of CdMoO4 was narrowed by the incorporation of a small amount of Ag nanoparticles. The surface plasmonic effect of Ag shows broad absorption in the visible region. The enhanced photocatalytic hydrogen production activities of all the samples were evaluated by using methanol as a sacrificial reagent in water under natural sunlight conditions. The results suggest that the rate of photocatalytic hydrogen production using CdMoO4 can be significantly improved by loading 2% Ag nanoparticles: i.e. 2465 µmol h-1 g-1 for a 15 mg catalyst. The strong excitation of surface plasmon resonance (SPR) absorption by the Ag nanoparticles was found in the Ag-loaded samples. In this system, the role of Ag nanoparticles on the surface of CdMoO4 has been discussed. In particular, the SPR effect is responsible for higher hydrogen evolution under natural sunlight because of broad absorption in the visible region. The current study could provide new insights for designing metal/semiconductor interface systems to harvest solar light for solar fuel generation.

Correction: Unique perforated graphene derived from Bougainvillea flowers for high-power supercapacitors: a green approach.

Correction for 'Unique perforated graphene derived from Bougainvillea flowers for high-power supercapacitors: a green approach' by Rajendra P. Panmand et al., Nanoscale, 2017, 9, 4801-4809.

Hierarchical CdMoO4 nanowire-graphene composite for photocatalytic hydrogen generation under natural sunlight.

Herein, a facile in situ solvothermal technique for the synthesis of a CdMoO4/graphene composite photocatalyst is reported. Graphene oxide (GO) was synthesised by an improved Hummers' method and was further used for the in situ synthesis of graphene via GO reduction and the formation of a CdMoO4 nanowire/graphene composite. The structural phase formation of tetragonal CdMoO4 was confirmed from X-ray diffraction measurements. The small nanoparticle assembled nanowires, prismatic microsphere morphology and crystalline nature of the synthesized material were investigated using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Due to its unique morphology and stability, the CdMoO4/graphene composite was used as a photocatalyst for H2O splitting. In comparison to pristine CdMoO4, the CdMoO4/graphene composite showed the best hydrogen evolution rate, i.e. 3624 µmole h-1 g-1, with an apparent quantum yield of 30.5%. The CdMoO4/graphene composite has a higher photocatalytic activity due to the inhibition of charge carrier recombination. H2 production measurements showed that the ternary semiconductor/graphene composite has enhanced photocatalytic activity for H2 generation.

Surface modified Li4Ti5O12 by paper templated approach for enhanced interfacial Li+ charge transfer in Li-ion batteries.

The Li4Ti5O12 (LTO) and lithium silicate (LS) surface modified LTO have been demonstrated by a unique paper templated method. Comparative study of structural characterization with electrochemical analysis was demonstrated for pristine and modified Li4Ti5O12. Structural and morphological study shows the existence of the cubic spinel structure with highly crystalline 250-300 nm size particles. The LS modified LTO shows the deposition of 10-20 nm sized LS nanoparticles on cuboidal LTO. Further, X-ray photoelectron spectroscopy (XPS) confirms the existence of Li2SiO3 (LS) in the modified LTO. The electrochemical performance was investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge. The modified LTO with 2% LS (LTS2) exhibited excellent rate capability compare to pristine LTO i.e. 182 mA h g-1 specific capacity at a current rate, 50 mA g-1 with remarkable cycling stability up to 1100 cycles at a current rate of 800 mA g-1. The lithium ion full cell of modified LTO with LS as an anode and LiCoO2 as a cathode exhibited a remarkably reversible specific capacity i.e. 110 mA h g-1. Both electronic and ionic conductivities of pristine LTO are observed to be enhanced by incorporation of appropriate amount of LS in LTO due to a larger surface contact at the interface of electrode and electrolyte. More significantly, the versatile paper templated synthesis approach of modified LTO with LS provides densely packed highly crystalline particles. Additionally, it exhibits lower Warburg coefficient and higher Li ion diffusion coefficient which in turn accelerate the interfacial charge transfer process, which is responsible for enhanced stable electrochemical performance. The detailed mechanism is expressed and elaborated for better understanding of enhanced electrochemical performance due to the surface modification.

Nanostructured N-doped orthorhombic Nb2O5 as an efficient stable photocatalyst for hydrogen generation under visible light.

The synthesis of orthorhombic nitrogen-doped niobium oxide (Nb2O5-xNx) nanostructures was performed and a photocatalytic study carried out in their use in the conversion of toxic H2S and water into hydrogen under UV-Visible light. Nanostructured orthorhombic Nb2O5-xNx was synthesized by a simple solid-state combustion reaction (SSCR). The nanostructural features of Nb2O5-xNx were examined by FESEM and HRTEM, which showed they had a porous chain-like structure, with chains interlocked with each other and with nanoparticles sized less than 10 nm. Diffuse reflectance spectra depicted their extended absorbance in the visible region with a band gap of 2.4 eV. The substitution of nitrogen in place of oxygen atoms as well as Nb-N bond formation were confirmed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. A computational study (DFT) of Nb2O5-xNx was also performed for investigation and conformation of the crystal and electronic structure. N-Substitution clearly showed a narrowing of the band gap due to N 2p bands cascading above the O 2p band. Considering the band gap in the visible region, Nb2O5-xNx exhibited enhanced photocatalytic activity toward hydrogen evolution (3010 µmol h-1 g-1) for water splitting and (9358 µmol h-1 g-1) for H2S splitting under visible light. The enhanced photocatalytic activity of Nb2O5-xNx was attributed to its extended absorbance in the visible region due to its electronic structure being modified upon doping, which in turn generates more electron-hole pairs, which are responsible for higher H2 generation. More significantly, the mesoporous nanostructure accelerated the supression of electron and hole recombination, which also contributed to the enhancement of its activity.

Growth study of hierarchical Ag3PO4/LaCO3OH heterostructures and their efficient photocatalytic activity for RhB degradation.

We have demonstrated the synthesis of Ag3PO4/LaCO3OH (APO/LCO) heterostructured photocatalysts by an in situ wet chemical method. From pre-screening evaluations of photocatalysts with APO/(x wt% LCO) composites with mass ratios of x = 5, 10, 15, 20, 25 and 30 wt%, we found that the APO/LCO (20 wt%) exhibited a superior photocatalytic activity for organic pollutant remediation. Therefore, an optimised photocatalyst APO/LCO (20 wt%) is selected for the present study and we investigate the effect of a mixed solvent system (H2O:THF) on the morphology, which has a direct effect on the photocatalytic performance. Interestingly, a profound effect on the morphological features of APO/LCO20 heterostructures was observed with variation in the ratio of the solvent system. From the FESEM study it is observed that the LCO spherical nanoparticles are transformed into nanorods with the variation of THF into the solvent system. Moreover, these LCO nanorods make intimate contact with the APO microstructures which is helpful for the improvement of the photocatalytic activity. The photocatalytic activities of the APO/LCO composites with different solvent ratios were evaluated by the degradation of rhodamine B (RhB) under visible light irradiation. Excellent photocatalytic activity was observed for the APO/LCO-2 (H2O : THF = 60 : 40) sample. This might be due to uniform covering of the APO microstructures by fine LCO rod-like structures offering intimate contact between the APO and LCO and providing proper channels for the degradation reactions. Furthermore, with an increasing THF volume ratio in the reaction system there was an increase of the dimensions of the LCO rod-like structures and also a loose compactness of their uniform intimate contact between the APO/LCO heterostructures. All in all, the enhanced photocatalytic activity of the APO/LCO heterostructures is attributed to the collective co-catalytic effect of LCO, by providing accelerated charge separation through the heterojunction interface, and THF, by helping to tune the unique morphological features which eventually facilitate the photocatalysis process.

Unique perforated graphene derived from Bougainvillea flowers for high-power supercapacitors: a green approach.

Herein, we demonstrated a green approach for the synthesis of high surface area (850 m2 g-1) mesoporous perforated graphene (PG) from Bougainvillea flower for the first time using a template free single-step method. The existence of PG was confirmed by XRD, Raman spectroscopy, FESEM, and FETEM. Surprisingly, FETEM clearly showed 5-10 nm perforation on the graphene sheets. More significantly, these mesoporous perforated graphene sheets can be produced in large scale using the present green approach. Considering high surface area and unique perforated graphene architecture, these PGs were studied for supercapacitor applications in detail without any chemical or physical activation. The nanoporosity and high conductivity of PG derived from Bougainvillea flower exhibited excellent supercapacitive performance. According to the supercapacitor study, the synthesized perforated graphene sheets conferred a very high specific capacitance of 458 F g-1 and an energy density of 63.7 Wh kg-1 at the power density of around 273.2 Wh kg-1 in aqueous 1 M Na2SO4. Significantly, the areal capacitance of PG was observed to be very high, i.e. 67.2 mF cm-2. The cyclability study results showed excellent stability of synthesized perforated graphene sheets up to 10 000 cycles. Note that the specific and areal capacitance and the energy density of the synthesized PGs are much higher than the earlier reported values. The high supercapacitive performance may be due to high surface area and mesoporosity of PG. The present approach has a good potential to produce cheaper and high surface area PG. These PGs are good candidates as an anode material in the lithium-ion battery.

Nanostructured CdS sensitized CdWO4 nanorods for hydrogen generation from hydrogen sulfide and dye degradation under sunlight.

In this report, CdS nanoparticles have been grown on the surface of CdWO4 nanorods via an in-situ approach and their high photocatalytic ability toward dye degradation and H2 evolution from H2S splitting under visible light has been demonstrated. The structural and optical properties as well as morphologies with varying amount of CdS to form CdS@CdWO4 have been investigated. Elemental mapping and high resolution transmission electron microscopy (HRTEM) analysis proved the sensitization of CdWO4 nanorods by CdS nanoparticles. A decrease in the PL emission of CdWO4 was observed with increasing amount of CdS nanoparticles loading possibly due to the formation of trap states. Considering the band gap in visible region, the photocatalytic study has been performed for H2 production from H2S and dye degradation under natural sunlight. The steady evolution of H2 was observed from an aqueous H2S solution even without noble metal. Moreover, the rate of photocatalytic H2 evolution over CdS modified CdWO4 is ca. 5.6 times higher than that of sole CdWO4 under visible light. CdS modified CdWO4 showed a good ability toward the photo-degradation of methylene Blue. The rate of dye degradation over CdS modified CdWO4 is ca. 7.4 times higher than that of pristine CdWO4 under natural sunlight. With increase in amount of CdS nanoparticle loading on CdWO4 nanorods the hydrogen generation was observed to be decreased where as dye degradation rate is increased. Such nano-heterostructures may have potential in other photocatalytic reactions.

Growth of Bi2Te3 quantum dots/rods in glass: a unique highly stable nanosystem with novel functionality for high performance magneto optical devices.

Magneto optical materials are currently of great interest, primarily for modern applications in optical isolation, modulation and switching in telecommunication. However, single crystals are the benchmark materials still used in these devices which are rather expensive and very difficult to fabricate. In this context, we are reporting herewith a stable and novel Bi(2)Te(3) quantum dot-glass nanosystem obtained using a controlled thermo-chemical method. The Q-dots of hexagonal Bi(2)Te(3) of size 4 to 14 nm were grown along the <1 1 3> direction. Surprisingly, we obtained quantum rods of Bi(2)Te(3) of size 6 × 10 nm for the first time. The strong quantum confinement in the nanosystem is clearly shown by the optical study. The band gap of the host glass was drastically reduced (from 4.00 to 1.88 eV) due to the growth of Bi(2)Te(3) quantum dots whereas photoluminescence showed a Stokes shift ~175 meV. Faraday Rotation (FR) investigations of the Bi(2)Te(3) quantum dot-glass nanosystem show a nonlinear response in Verdet constant with a decrease in the Bi(2)Te(3) dot sizes. The Bi(2)Te(3) Q-dot-glass nanosystem with ~4 nm dots shows significant enhancement (70 times) in Verdet constant compared to the host glass and more radically better than conventional single crystal (TGG). This is the first time that such a type of unique nanosystem has been architectured and has given extremely good magneto-optical performance. We strongly feel that this novel nanosystem has tremendous applications in magneto-optical devices. It is noteworthy that expensive single crystals can be replaced with this cost effective novel glass nanosystem. Interestingly, the present quantum dot-glass nanosystem can be transformed into optical fibers very easily, which will have an exceptionally high impact on the fabrication of high performance magneto optical devices.