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.

CdS decorated MnWO4 nanorod nanoheterostructures: a new 0D-1D hybrid system for enhanced photocatalytic hydrogen production under natural sunlight.

Constructing a heterostructure is an effective strategy to reduce the electron-hole recombination rate, which enhances photocatalytic activity. Here, we report a facile hydrothermal method to grow CdS nanoparticles on MnWO4 nanorods and their photocatalytic hydrogen generation under solar light. A structural study shows the decoration of hexagonal CdS nanoparticles on monoclinic MnWO4. Morphological studies based on FE-TEM analysis confirm the sensitization of CdS nanoparticles (10 nm) on MnWO4 nanorods of diameter-35 nm with mean length ∼100 nm. The lower PL intensity of MnWO4 was observed with an increasing amount of CdS nanoparticles, which shows inhibition of the charge carrier recombination rate. A CdS@MnWO4 narrow band gap semiconductor was employed for photocatalytic hydrogen generation from water under solar light and the highest amount of hydrogen, i.e. 3218 µmol h-1 g-1, is obtained which is 21 times higher than that with pristine MnWO4. The enhanced photocatalytic activity is ascribed to the formation of a CdS@MnWO4 nanoheterostructure resulting in efficient spatial separation of photogenerated electron-hole pairs due to vacancy defects. More significantly, direct Z-scheme electron transfer from MnWO4 to CdS is responsible for the enhanced hydrogen evolution. This work signifies that a CdS decorated MnWO4 nanoheterostructure has the potential to improve the solar to direct fuel conversion efficiency.

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.

A nanostructured SnO2/Ni/CNT composite as an anode for Li ion batteries.

A SnO2/Ni/CNT nanocomposite was synthesized using a simple one-step hydrothermal method followed by calcination. A structural study via XRD shows that the tetragonal rutile structure of SnO2 is maintained. Further, X-ray photoelectron spectroscopy (XPS) and Raman studies confirm the existence of SnO2 along with CNTs and Ni nanoparticles. The electrochemical performance was investigated via cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge measurements. The nanocomposite has been used as an anode material for lithium-ion batteries. The SnO2/Ni/CNT nanocomposite exhibited an initial discharge capacity of 5312 mA h g-1 and a corresponding charge capacity of 2267 mA h g-1 during the first cycle at 50 mA g-1. Pristine SnO2 showed a discharge/charge capacity of 1445/636 mA h g-1 during the first cycle at 50 mA g-1. This clearly shows the effects of the optimum concentrations of CNTs and Ni. Further, the nanocomposite (SnNiCn) shows a discharge capacity as high as 919 mA h g-1 after 210 cycles at a current density of 400 mA g-1 in a Li-ion battery set-up. Thus, the obtained capacity from the nanocomposite is much higher compared to pristine SnO2. The higher capacity in the nanoheterostructure is due to the well-dispersed nanosized Ni-decorated stabilized SnO2 along with the CNTs, avoiding pulverization as a result of the volumetric change of the nanoparticles being minimized. The material accommodates huge volume expansion and avoids the agglomeration of nanoparticles during the lithiation and delithiation processes. The Ni nanoparticles can successfully inhibit Sn coarsening during cycling, resulting in the enhancement of stability during reversible conversion reactions. They ultimately enhance the capacity, giving stability to the nanocomposite and improving performance. Additionally, the material exhibits a lower Warburg coefficient and higher Li ion diffusion coefficient, which in turn accelerate the interfacial charge transfer process; this is also responsible for the enhanced stable electrochemical performance. A detailed mechanism is expressed and elaborated on to provide a better understanding of the enhanced electrochemical performance.

Unique N doped Sn3O4 nanosheets as an efficient and stable photocatalyst for hydrogen generation under sunlight.

Unique N doped Sn3O4 nanosheets have been demonstrated successfully using a facile hydrothermal method. Investigations of the triclinic phase and the impurities were performed using powder X-ray diffraction analysis (XRD) and Raman spectroscopy. The morphological analysis demonstrated a rectangular intra- and inter-connected nanosheet-like structure. The length of the nanosheets was observed to be in the range of 200-300 nm and the thickness of the nanosheets was less than 10 nm. The optical study reveals an extended absorption edge into the visible region, owing to the incorporation of nitrogen into the lattice of Sn3O4, which was further confirmed using X-ray photoelectron spectroscopy (XPS). Considering the band structure in the visible region, the photocatalytic activities of pristine and N doped Sn3O4 nanosheets for hydrogen evolution from water under natural sunlight were investigated. 4% N-Sn3O4 showed a higher photocatalytic activity (654.33 µmol-1 h-1 0.1 g-1) for hydrogen production that was eight times that of pristine Sn3O4. The enhanced photocatalytic activity is attributed to the inhibition of charge carrier separation owing to the N doping, morphology and crystallinity of the N-Sn3O4 nanostructures. A stable efficiency was observed for three cycles, which clearly shows the stability of N-Sn3O4.

A hierarchical SnS@ZnIn2S4 marigold flower-like 2D nano-heterostructure as an efficient photocatalyst for sunlight-driven hydrogen generation.

Herein, we report the in situ single-step hydrothermal synthesis of hierarchical 2D SnS@ZnIn2S4 nano-heterostructures and the examination of their photocatalytic activity towards hydrogen generation from H2S and water under sunlight. The photoactive sulfides rationally integrate via strong electrostatic interactions between ZnIn2S4 and SnS with two-dimensional ultrathin subunits, i.e. nanopetals. The morphological study of nano-heterostructures revealed that the hierarchical marigold flower-like structure is self-assembled via the nanopetals of ZnIn2S4 with few layers of SnS nanopetals. Surprisingly, it also showed that the SnS nanopetals with a thickness of ∼25 nm couple in situ with the nanopetals of ZnIn2S4 with a thickness of ∼25 nm to form a marigold flower-like assembly with intimate contact. Considering the unique band gap (2.0-2.4 eV) of this SnS@ZnIn2S4, photocatalytic hydrogen generation from water and H2S was performed under sunlight. SnS@ZnIn2S4 exhibits enhanced hydrogen evolution, i.e. 650 µmol h-1 g-1 from water and 6429 µmol h-1 g-1 from H2S, which is much higher compared to that of pure ZnIn2S4 and SnS. More significantly, the enhancement in hydrogen generation is 1.6-2 times more for H2S splitting and 6 times more for water splitting. SnS@ZnIn2S4 forms type I band alignment, which accelerates charge separation during the surface reaction. Additionally, this has been provoked by the nanostructuring of the materials. Due to the nano-heterostructure with hierarchical morphology, the surface defects increased which ultimately suppresses the recombination of the electron-hole pair. The above-mentioned facts demonstrate a significant improvement in the interface electron transfer kinetics due to such a unique 2D nano-heterostructure semiconductor which is responsible for a higher photocatalytic activity.

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.

ZnO decorated Sn3O4 nanosheet nano-heterostructure: a stable photocatalyst for water splitting and dye degradation under natural sunlight.

Herein, a facile hydrothermally-assisted sonochemical approach for the synthesis of a ZnO decorated Sn3O4 nano-heterostructure is reported. The phase purity of the nano-heterostructure was confirmed by X-ray diffraction and Raman spectroscopy. The morphological analysis demonstrated a nanosheet-like structure of Sn3O4 with a thickness of 20 nm, decorated with ZnO. The optical band gap was found to be 2.60 eV for the ZnO@Sn3O4 nano-heterostructure. Photoluminescence studies revealed the suppression of electron-hole recombination in the ZnO@Sn3O4 nano-heterostructure. The potential efficiency of ZnO@Sn3O4 was further evaluated towards photocatalytic hydrogen production via H2O splitting and degradation of methylene blue (MB) dye. Interestingly, it showed significantly superior photocatalytic activity compared to ZnO and Sn3O4. The complete degradation of MB dye solution was achieved within 40 min. The nano-heterostructure also exhibited enhanced photocatalytic activity towards hydrogen evolution (98.2 µmol h-1/0.1 g) via water splitting under natural sunlight. The superior photocatalytic activity of ZnO@Sn3O4 was attributed to vacancy defects created due to its nano-heterostructure.

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.

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.

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.