Nanostructured electroless Ni deposited SnO2 for solar hydrogen production.

Herein, Ni-decorated SnO2 (Ni@SnO2) nanostructures have been synthesized using SnO2 as a matrix via a simple electroless deposition method for the generation of hydrogen, a potent near-future fuel. XRD analysis confirmed the generation of rutile SnO2 in Ni@SnO2. FESEM and FETEM imaging exhibited the formation of SnO2 nanoparticles with a size of 10-50 nm, which are deposited with Ni nanoparticles (5-7 nm) and intermittent films (thickness 1-2 nm). The associated EDS elemental mapping validated Ni deposition on the surface of the SnO2 nanoparticles, further supplemented by FTIR, Raman and XPS analysis. Slight red shifts in the band gaps of the Ni@SnO2 nanostructures (in the range of 3.53-3.65 eV) compared to the pristine SnO2 nanoparticles (3.72 eV) were observed. Also, intensity quenching of the band gap and associated defect peaks were observed in PL analysis. The Ni@SnO2 nanostructures were used as photocatalysts and exhibited proficient hydrogen evolution. Among the samples, the 0.3 wt% Ni@SnO2 nanostructures showed the greatest hydrogen evolution, i.e., ∼50 µmol g-1 h-1 under visible light irradiation versus pristine SnO2 (8.5 µmol g-1 h-1) owing to the enhanced density of active sites and effective charge separation. It is noteworthy that the hydrogen evolution is much better as compared to earlier reports of Pt-doped-SnO2 based materials.

Microstructure tuned Na3V2(PO4)3@C electrodes toward ultra-long-life sodium-ion batteries.

Sodium-ion batteries (SIBs) are emerging as the best replacement for Li-ion batteries. In this regard, research on developing a reliable cathode material for SIBs is burgeoning. Rhombohedral Na3V2(PO4)3 (NVP), is a typical sodium super ionic conductor (NASICON) type material having prominent usage as a cathode material for SIBs. In this study, we prepared an NVP@C composite using a one-step hydrothermal method (at 180 °C) and consecutively calcined at different temperatures (750, 800, 850, and 900 °C). All the samples were thoroughly characterized and the changes in the crystal structure and particle size distribution were investigated using a Rietveld refinement method. NVP calcined at 850 °C exhibits the best battery performance with a discharge capacity of 94 mA h g-1 and retention up to 90% after 250 cycles at 2C. It also exhibits remarkable cycling stability with 94% (63 mA h g-1) retention after 2000 cycles at high-rate endurance (10C). The observed electrochemical performances of the samples were correlated with improved electrical conductivity due to the conductive carbon mixing with Na3V2(PO4)3 and enhancement in the crystallinity.

Solid state engineering of Bi2S3/rGO nanostrips: an excellent electrode material for energy storage applications.

The study presents a novel, one-pot, and scalable solid-state reaction scheme to prepare bismuth sulphide (Bi2S3)-reduced graphene oxide (rGO) nanocomposites using bismuth oxide (Bi2O3), thiourea (TU), and graphene oxide (GO) as starting materials for energy storage applications. The impact of GO loading concentration on the electrochemical performance of the nanocomposites was investigated. The reaction follows a diffusion substitution pathway, gradually transforming Bi2O3 powder into Bi2S3 nanostrips, concurrently converting GO into rGO. Enhanced specific capacitances were observed across all nanocomposite samples, with the Bi2S3@0.2rGO exhibiting the highest specific capacitance of 705 F g-1 at a current density of 1 A g-1 and maintaining a capacitance retention of 82% after 1000 cycles. The superior specific capacitance is attributed to the excellent homogeneity and synergistic relation between rGO and Bi2S3 nanostrips. This methodology holds promise for extending the synthesis of other chalcogenides-rGO nanocomposites.

In situ synthesis of g-C3N4/Ti3C2Tx nano-heterostructures for enhanced photocatalytic H2 generation via water splitting.

Herein, we demonstrated the in situ synthesis of g-C3N4/Ti3C2Tx nano-heterostructures for hydrogen generation under UV visible light irradiation. The formation of the g-C3N4/Ti3C2Tx nano-heterostructures was confirmed via powder X-ray diffraction and supported by XPS. The FE-SEM images indicated the formation of layered structures of MXene and g-C3N4. HR-TEM images and SAED patterns confirmed the presence of g-C3N4 together with Ti3C2Tx nanosheets, i.e., the formation of nano-heterostructures of g-C3N4/Ti3C2Tx. The absorption spectra clearly showed the distinct band gaps of g-C3N4 and Ti3C2Tx in the nano-heterostructure. The increase in PL intensity and broadening of the peak with an increase in g-C3N4 indicated the suppression of electron-hole recombination. Furthermore, the nano-heterostructure was used as a photocatalyst for H2 generation from water and methylene blue dye degradation. The highest H2 evolution (1912.25 µmol/0.1 g) with good apparent quantum yield (3.1%) and an efficient degradation of MB were obtained for gCT-0.75, which was much higher compared to that of the pristine materials. The gCT-0.75 nano-heterostructure possessed a high surface area and abundant vacancy defects, facilitating the separation of charge carriers, which was ultimately responsible for this high photocatalytic activity. Additionally, TRPL clearly showed a higher decay time, which supports the enhancement in the photocatalytic activity of the gCT-0.75 nano-heterostructure. The nano-heterostructure with the optimum concentration of g-C3N4 formed a hetero-junction with the linked catalytic system, which facilitated efficient charge carrier separation also responsible for the enhanced photocatalytic activity.

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.

Highly Stable MWCNT@NVP Composite as a Cathode Material for Na-Ion Batteries.

A 3D framework with Nasicon structured polyanionic Na3V2(PO4)3 (NVP) has been emphasized as a leading cathode material for sodium-ion batteries (SIBs) due to its high working voltage plateau, structural stability, and good rate performance. Herein, pristine NVP and MWCNT@NVP composite synthesized via a facile solid-state method are examined and compared as cathode materials for Na-ion batteries. The morphological study confirms the uniform distribution of MWCNTs in the pristine NVP structure. Impedance spectroscopy clearly confirms more diffusion of Na ions for the MWCNT@NVP composite as compared to pristine NVP, considering its diffusion coefficient which directly implies on an increase in specific capacity. MWCNT@NVP (FNV-2) showed specific discharge capacity 110 mAhg-1 at 0.1C current rate which is almost stable at higher current rates with marginal fading. However, the pristine NVP shows capacity loss at a higher current rate. It is noteworthy that the MWCNT@NVP composite shows stable performance with marginal specific capacity fading (1%) compared to pristine (15%). This is because of the mechanical integrity and stability afforded to the composite by the intertwined MWCNT framework in the MWCNT@NVP composite matrix against electrode degradation during the electrochemical reaction. More significantly, even at a higher current rate, that is, at 10 C, the composite recorded a very stable and excellent Columbic efficiency of 97% with a reversible specific capacity of 94 mAhg-1 after 2000 cycles. An enhanced electrochemical performance, that is, rate capability and cycling stability, demonstrates the high potential of the MWCNT@NVP composite for Na-ion storage. Moreover, a sodium-ion full cell with hard carbon demonstrated a reversible capacity of 103 mAhg-1 at C/20 current rate, which clearly demonstrates that MWCNT@NVP is a promising cathode material for sodium-ion batteries.

Electroless Ni plated nanostructured TiO2 as a photocatalyst for solar hydrogen production.

Herein, we have demonstrated a facile electroless Ni coated nanostructured TiO2 photocatalyst for the first time. More significantly the photocatalytic water splitting shows excellent performance for hydrogen production which is hitherto unattempted. The structural study exhibits majorly the anatase phase along with the minor rutile phase of TiO2. Interestingly, electroless nickel deposited on the TiO2 nanoparticles of size 20 nm shows a cubic structure with nanometer scale Ni coating (1-2 nm). XPS supports the existence of Ni without any oxygen impurity. The FTIR and Raman studies support the formation of TiO2 phases without any other impurities. The optical study shows a red shift in the band gap due to optimum nickel loading. The emission spectra show variation in the intensity of the peaks with Ni concentration. The vacancy defects are pronounced in lower concentrations of Ni loading which shows the formation of a huge number of charge carriers. The electroless Ni loaded TiO2 has been used as a photocatalyst for water splitting under solar light. The primary results manifest that the hydrogen evolution of electroless Ni plated TiO2 is 3.5 times higher (1600 µmol g-1 h-1) than pristine TiO2 (470 µmol g-1 h-1). As shown in the TEM images, nickel is completely electroless plated on the TiO2 surface, which accelerates the fast transport of electrons to the surface. It suppresses the electron-hole recombination drastically which is responsible for higher hydrogen evolution using electroless Ni plated TiO2. The recycling study exhibits a similar amount of hydrogen evolution at similar conditions which shows the stability of the Ni loaded sample. Interestingly, Ni powder loaded TiO2 did not show any hydrogen evolution. Hence, the approach of electroless plating of nickel over the semiconductor surface will have potential as a good photocatalyst for hydrogen evolution.

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.

Ni loaded SnS2 hexagonal nanosheets for photocatalytic hydrogen generation via water splitting.

Herein we have prepared the Ni-decorated SnS2 nanosheets with varying concentrations of Ni from 1 to 10 mol% (1, 2.5, 5, and 10 mol%) and studied their various physicochemical and photocatalytic properties. The chemical reduction technique was utilized to load the Ni nanoparticles on SnS2 nanosheets. The synthesized Ni decorated SnS2 (denoted as Ni-SnS2) was characterized using different spectroscopic techniques such as X-ray diffraction, diffuse reflectance UV-vis and photoluminescence spectroscopy, field emission scanning electron microscopy (FESEM), and field emission transmission electron microscopy (FETEM). XRD revealed the formation of the highly crystalline hexagonal phase of SnS2 but for nickel loading there is no additional peak observed. Further, the as-prepared Ni-SnS2 nano-photocatalyst shows absorption behaviour in the visible region, and photoluminescence spectra of the Ni-SnS2 nanostructures show band edge emission centred at 524 nm, and the peak intensity decreases with Ni loading. The FE-SEM and FE-TEM confirm the formation of hexagonal sheets having evenly distributed Ni nanoparticles of size ∼5-10 nm. BET surface area analysis was observed to be enhanced with Ni loading. The photocatalytic performance of the prepared Ni-SnS2 nanosheets was evaluated for hydrogen generation via water splitting under a 400 W mercury vapour lamp. Among the prepared Ni-SnS2 nanostructures, the Ni loaded with 2.5 mol% provided the highest hydrogen production i.e., 1429.2 µmol 0.1 g-1 (% AQE 2.32) in four hours, almost 1.6 times that of pristine SnS2 i.e., 846 µmol 0.1 g-1. Furthermore, the photocatalytic performance of the catalyst is also correlated with the photoconductivity by measuring the photocurrent. The photoconductivity of the samples is revealed to be stable and the conductivity of 2.5 mol% Ni-SnS2 is higher i.e. 20 times that of other Ni-SnS2 and pristine SnS2 catalysts.

GenSLMs: Genome-scale language models reveal SARS-CoV-2 evolutionary dynamics.

We seek to transform how new and emergent variants of pandemic-causing viruses, specifically SARS-CoV-2, are identified and classified. By adapting large language models (LLMs) for genomic data, we build genome-scale language models (GenSLMs) which can learn the evolutionary landscape of SARS-CoV-2 genomes. By pre-training on over 110 million prokaryotic gene sequences and fine-tuning a SARS-CoV-2-specific model on 1.5 million genomes, we show that GenSLMs can accurately and rapidly identify variants of concern. Thus, to our knowledge, GenSLMs represents one of the first whole genome scale foundation models which can generalize to other prediction tasks. We demonstrate scaling of GenSLMs on GPU-based supercomputers and AI-hardware accelerators utilizing 1.63 Zettaflops in training runs with a sustained performance of 121 PFLOPS in mixed precision and peak of 850 PFLOPS. We present initial scientific insights from examining GenSLMs in tracking evolutionary dynamics of SARS-CoV-2, paving the path to realizing this on large biological data.

Biofilm inhibition in Candida albicans with biogenic hierarchical zinc-oxide nanoparticles.

The present study demonstrates lignin (L), fragments of lignin (FL), and oxidized fragmented lignin (OFL) as templates for the synthesis of zinc oxide nanoparticles (ZnO NPs) viz., lignin-ZnO (L-ZnO), hierarchical FL-ZnO, and OFL-ZnO NPs. The X-ray diffraction patterns confirmed the formation of phase pure ZnO NPs with a hexagonal wurtzite structure. Electron microscopy confirmed the hierarchical structures with one-dimensional arrays of ZnO NPs with an average particle diameter of 40 nm. The as-synthesized L-ZnO, FL-ZnO, and OFL-ZnO NPs were tested in-vitro for growth and virulence inhibition (morphogenesis and biofilm) in Candida albicans. L-ZnO, FL-ZnO, and OFL-ZnO NPs all inhibited growth and virulence. Growth and virulence inhibitions were highest (more than 90%, respectively at 125, 31.2, and 62.5 µg/mL) in presence of FL-ZnO NPs, indicating that the hierarchical FL-ZnO NPs were potent growth and virulence inhibiting agent than non-hierarchical ZnO NPs. Furthermore, the real-time polymerase chain (RT-PCR) was used to study the virulence inhibition molecular mechanisms of L-ZnO, FL-ZnO, and OFL-ZnO NPs. RT-PCR results showed that the downregulation of phr1, phr2, efg1, hwp1, ras1, als3 and als4, and the upregulation of bcy1, nrg1, and tup1 genes inhibited the virulence in C. albicans. Lastly, we also performed in-vitro test cell cytotoxicity on the cell line, mouse embryo 3T3L1, and in-vivo toxicity on Rats, which showed that FL-ZnO NPs were biocompatible and nontoxic.

Polyaniline-wrapped MnMoO4 as an active catalyst for hydrogen production by electrochemical water splitting.

Developing efficient, low-cost, and environment-friendly electrocatalysts for hydrogen generation is critical for lowering energy usage in electrochemical water splitting. Moreover, for commercialization, fabricating cost-efficient, earth-abundant electrocatalysts with superior characteristics is of urgent need. Towards this endeavor, we report the synthesis of PANI-MnMoO4 nanocomposites using a hydrothermal approach and an in situ polymerization method with various concentrations of MnMoO4. The fabricated nanocomposite electrocatalyst exhibits bifunctional electrocatalytic activity towards the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) at a lower overpotential of 410 mV at 30 mA cm-2 and 155 mV at 10 mA cm-2, respectively in an alkaline electrolyte. Furthermore, while showing overall water splitting (OWS) performance, the optimized PM-10 (PANI-MnMoO4) electrode reveals the most outstanding OWS performance with a lower cell voltage of 1.65 V (vs. RHE) at a current density of 50 mA cm-2 with an excellent long-term cell resilience of 24 h.

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.

Synergetic Strategy for the Fabrication of Self-Standing Distorted Carbon Nanofibers with Heteroatom Doping for Sodium-Ion Batteries.

Currently, the limited availability of lithium sources is escalating the cost of lithium-ion batteries (LIBs). Considering the fluctuating economics of LIBs, sodium-ion batteries (SIBs) have now drawn attention because sodium is an earth-abundant, low-cost element that exhibits similar chemistry to that of LIBs. Despite developments in different anode materials, there still remain several challenges in SIBs, including lighter cell design for SIBs. The presented work designs a facile strategy to prepare nitrogen-doped free-standing pseudo-graphitic nanofibers via electrospinning. A structural and morphological study implies highly disordered graphitic structured nanofibers having diameters of ∼120-170 nm, with a smooth surface. X-ray photoelectron spectroscopy analysis showed that nitrogen was successfully doped in carbon nanofibers (CNFs). When served as an anode material for SIBs, the resultant material exhibits excellent sodium-ion storage properties in terms of long-term cycling stability and high rate capability. Notably, a binder-free self-standing CNF without a current collector was used as an anode for SIBs that delivered capacities of 210 and 87 mA h g-1 at 20 and 1600 mA g-1, respectively, retaining a capacity of 177 mA h g-1 when retained at 20 mA g-1. The as-synthesized CNFs demonstrate a long cycle life with a relatively high Columbic efficiency of 98.6% for the 900th cycle, with a stable and excellent rate capacity. The sodium storage mechanisms of the CNFs were examined with various nitrogen concentrations and carbonization temperatures. Furthermore, the diffusion coefficients of the sodium ions based on the electrochemical impedance spectra measurement have been calculated in the range of 10-15-10-12 cm2 s-1, revealing excellent diffusion mobility for Na atoms in the CNFs. This study demonstrates that optimum nitrogen doping and carbonization temperature demonstrated a lower Warburg coefficient and a higher Na-ion diffusion coefficient leads to enhanced stable electrochemical performance. Thus, our study shows that the nitrogen-doped CNFs will have potential for SIBs.

Cobalt-Doped Manganese Dioxide Hierarchical Nanostructures for Enhancing Pseudocapacitive Properties.

Herein, overall improvement in the electrochemical performance of manganese dioxide is achieved through fine-tuning the microstructure of partially Co-doped manganese dioxide nanomaterial using facile hydrothermal method with precise control of preparative parameters. The structural investigation exhibits formation of a multiphase compound accompanied by controlled reflections of α-MnO2 as well as γ-MnO2 crystalline phases. The morphological examination manifests the presence of MnO2 nanowires having a width of 70-80 nm and a length of several microns. The Co-doped manganese dioxide electrode displayed a particular capacitive behavior along with a rising order of capacitance concerning with increased cobalt ion concentration suitable for certain limits. The value of specific capacitance achieved by a 5% Co-doped manganese dioxide sample was 1050 F g-1 at 0.5 A g-1, which was nearly threefold greater than that achieved by a bare manganese dioxide electrode. Furthermore, Co-doped manganese dioxide nanocomposite electrode exhibits exceptional capacitance retention (92.7%) till 10,000 cycles. It shows the good cyclability as well as stability of the material. Furthermore, we have demonstrated the solid-state supercapacitor with good energy and power density.

Highly crystalline anatase TiO2 nanocuboids as an efficient photocatalyst for hydrogen generation.

Highly crystalline anatase titanium dioxide (TiO2) nanocuboids were synthesized via a hydrothermal method using ethylenediamine tetraacetic acid as a capping agent. The structural study revealed the nanocrystalline nature of anatase TiO2 nanocuboids. Morphological study indicates the formation of cuboid shaped particles with thickness of ∼5 nm and size in the range of 10-40 nm. The UV-visible absorbance spectra of TiO2 nanocuboids showed a broad absorption with a tail in the visible-light region which is attributed to the incorporation of nitrogen atoms into the interstitial positions of the TiO2 lattice as well as the formation of carbonaceous and carbonate species on the surface of TiO2 nanocuboids. The specific surface areas of prepared TiO2 nanocuboids were found to be in the range of 85.7-122.9 m2 g-1. The formation mechanism of the TiO2 nanocuboids has also been investigated. Furthermore, the photocatalytic activities of the as-prepared TiO2 nanocuboids were evaluated for H2 generation via water splitting under UV-vis light irradiation and compared with the commercial anatase TiO2. TiO2 nanocuboids obtained at 200 °C after 48 h exhibited higher photocatalytic activity (3866.44 µmol h-1 g-1) than that of commercial anatase TiO2 (831.30 µmol h-1 g-1). The enhanced photoactivity of TiO2 nanocuboids may be due to the high specific surface area, good crystallinity, extended light absorption in the visible region and efficient charge separation.

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.

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.

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.