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.

Controlled synthesis of monodispersed ZnSe microspheres for enhanced photo-catalytic application and its corroboration using density functional theory.

The present work reports enhanced photocatalytic performance of highly crystalline, monodisperse ZnSe microspheres, synthesized by the size-selective, ETDA-assisted hydrothermal method. Systematic studies on time-dependent reaction kinetics and growth parameters indicate dependency of morphology and crystal structure on the volume % of EDTA and dependency of size on the volume % of hydrazine hydrate for ZnSe microspheres. X-ray diffraction studies confirm highly crystalline cubic zinc blende crystal structure with crystallite size in the range of 10-15 nm. Diffuse reflectance spectra show blue shift having a broad absorption peak between 415 and 425 nm, with a band gap of ∼2.6 eV from the K-M plot. Photoluminescence spectra show higher ratio of near band edge emission to deep level emission, confirming the decrease in defect related emission and depicting the higher crystallinity of ZnSe. Raman spectroscopy also confirms the crystalline and pure nature of ZnSe microspheres, from the observation of a high intensity dominant peak at 248 cm-1, attributed to longitudinal optical phonon scattering. Morphological analysis using FE-SEM and HRTEM shows monodispersed microspheres having size ∼2.5 µm, made up of small ZnSe nanocrystals with ∼10 nm size and with an interplanar spacing of ∼0.32 nm, corresponding to zinc blende ZnSe(111) planes. Brunauer-Emmett-Teller analysis indicates type-IV adsorption-isotherms and hysteresis loops, confirming the presence of mesopores on the surface of ZnSe microspheres controlling the diffusion rate of the catalyst. The degradation rate constant for methylene-blue using first-order reaction kinetics confirms improvement in photocatalytic activity by a factor of 7 to 13 times higher than that of bulk ZnSe, which is attributed to the controlled, well-defined morphology of spherical microstructures made up of small-sized ZnSe nanocrystals. Density functional theory based calculations support the preferential adsorption of EDTA at the Se site of the ZnSe(111) surface with an energy of -1.90 eV. The electronic-structure plot demonstrates semiconducting behaviour with a direct band gap of ∼1.51 eV. First-principles calculations confirm enhancement in the photocatalytic water splitting activity of the ZnSe(111) surface via adsorption of intermediates. The improvement in dye degradation can be attributed to the enhanced oxidation process through the formation of intermediates such as O* (-3.13 eV) and HO* (-2.57 eV) at the Se site of the ZnSe surface.

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.

Hydrothermal Generation of 3-Dimensional WO3 Nanocubes, Nanobars and Nanobricks, Their Antimicrobial and Anticancer Properties.

In our current endeavor, 3-dimensional (3D) tungsten oxide (WO3) nanostructures (nanocubes, nanobars and nanobricks) have been swiftly generated via hydrothermal route at 160 °C for 24 h. Physico-chemical characterization of the resultant powder revealed formation of WO3 nanostructures with predominantly faceted cube, brick and rectangular bar-like morphology. The present study was also aimed at exploring the antimicrobial and anticancer potential of WO3 nanostructures. Antimicrobial activity was tested against different micro-organisms viz., Pseudomonas aeruginosa, Staphylococcus aureus, Klebsiella pneumoniae, Escherichia coli and Aspergillus fumigatus. The antibacterial and antifungal activity was ascertained against these micro-organisms by measuring the diameter of inhibition zone in agar well diffusion test which revealed that the resultant WO3 nanostructures acted as excellent antibacterial agents against both bacteria and fungi but were more effective against the fungus, A. fumigatus. To examine the growth curves of bacterial cells, time kill assay was monitored for E. coli, against which significant antibacterial action of WO3 nanostructures was noted. The anti-cancer activity of WO3 nanostructures was found to be concentration-dependent against KB cell line by viable cell count method. In our pilot study, WO3 nanostructures suspension with concentration in the range of 10-1 to 10-5 mg/ml was found to kill KB cells effectively.

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.

Sol-Gel Assisted Isotropic Morphological Progression in Nanostructured MoO3 and Allied Investigations on Photocatalytic Dye-Degradation.

We report tunable-morphology oriented facile yet scalable route to synthesize 1D (nanorod) and 2D (nanobelt) MoO3 nanostructures at gram scale using conventional as well as sonochemistry assisted sol-gel technique. The structural, morphological and optical properties of the samples can be befittingly altered by varying the synthesis protocol. The resultant orthorhombic MoO3 nanomorphs demonstrated efficient and expeditious photocatalytic degradation of the pollutant dye, Methylene Blue (MB). We have observed that appreciable photocatalytic MB dye-degradation can be accomplished within 30 minutes with high rate constants of 0.0786 min-1 and 0.233 min-1 for rod and belt-like MoO3-nanostructures, respectively. The pilot results indicate that the resultant MoO3 nanomorphs can be potentially used as solar light driven industrial photocatalyst material with their intrinsic photostability.

Swift tuning from spherical molybdenum microspheres to hierarchical molybdenum disulfide nanostructures by switching from solvothermal to hydrothermal synthesis route.

Herein, we report the synthesis of metallic molybdenum microspheres and hierarchical MoS2 nanostructures by facile template-free solvothermal and hydrothermal approach, respectively. The morphological transition of the Mo microspheres to hierarchical MoS2 nanoflower architectures is observed to be accomplished with change in solvent from ethylenediamine to water. The resultant marigold flower-like MoS2 nanostructures are few layers thick with poor crystallinity while spherical ball-like molybdenum microspheres exhibit better crystalline nature. This is the first report pertaining to the synthesis of Mo microspheres and MoS2 nanoflowers without using any surfactant, template or substrate in hydro/solvothermal regime. It is opined that such nanoarchitectures of MoS2 are useful candidates for energy related applications such as hydrogen evolution reaction, Li ion battery and pseudocapacitors. Inquisitively, metallic Mo can potentially act as catalyst as well as fairly economical Surface Enhanced Raman Spectroscopy (SERS) substrate in biosensor applications.

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.

CO2 Laser Direct Written MOF-Based Metal-Decorated and Heteroatom-Doped Porous Graphene for Flexible All-Solid-State Microsupercapacitor with Extremely High Cycling Stability.

Over the past decade, flexible and wearable microelectronic devices and systems have gained significant importance. Because portable power source is an essential need of such wearable devices, currently there is considerable research emphasis on the development of planar interdigitated micro energy -torage devices by employing diverse precursor materials to obtain functional materials (functional carbon, oxides, etc.) with the desirable set of properties. Herein we report for the first time the use of metal organic framework (MOF) and zeolitic imidazolate framework (ZIF-67) for high-wavelength photothermal laser direct writing of metal-decorated, heteroatom-doped, porous few-layer graphene electrodes for microsupercapacitor application. We argue that the specific attributes of MOF as a precursor and the high-wavelength laser writing approach (which creates extremely high localized and transient temperature (>2500 °C) due to strong absorption by lattice vibrations) are together responsible for the peculiar interesting properties of the carbon material thus synthesized, thereby rendering extremely high cycling stability to the corresponding microsupercapacitor device. Our device exhibits near 100% retention after 200 000 cycles as well as stability under 150° bending.

Nanoscale Mo- MoO3 Entrapped in Engineering Thermoplastic: Inorganic Pathway to Bactericidal and Fungicidal Action.

In our contemporary endeavor, metallic molybdenum (Mo) and semiconducting molybdenum trioxide (MoO3) nanostructures have been simultaneously generated via solid state reaction between molybdenum (III) chloride (MoCl3) and polyphenylene sulfide (PPS) at 285 (°)C in unimolar ratio for different time durations, namely, 6 h, 24 h, and 48 h. The resultant nanocomposites (NCs) revealed formation of predominantly metallic Mo for all the samples. However, MoO3 gradually gained prominent position as secondary phase with rise in reaction time. The present study was intended to investigate the antibacterial potential of metal-metal oxide-polymer NCs, i.e., Mo- MoO3-PPS against microorganisms, viz., Pseudomonas aeruginosa, Staphylococcus aureus, Klebsiella pneumoniae, and Aspergillus fumigatus. The antibacterial activity of the NCs was evaluated by agar well diffusion investigation. Maximum sensitivity concentrations of NCs were determined by finding out minimum inhibitory concentration (MIC) and minimum bactericidal/fungicidal concentration (MBC/MFC). Moreover, the NCs prepared at reaction time of 48 h exhibited best MBC values and were tested with time kill assay which revealed that the growth of S. aureus was substantially inhibited by Mo- MoO3-PPS NCs. This synchronized formation of Mo- MoO3 nanostructures in an engineering thermoplastic may have potential antimicrobial applications in biomedical devices and components. Prima facie results on antifungal activity are indicative of the fact that these materials can show anti-cancer behavior.

Antimicrobial properties of uncapped silver nanoparticles synthesized by DC arc thermal plasma technique.

We, herein, report the antimicrobial properties of uncapped silver nanoparticles for a Gram positive model organism, Bacillus subtilis. Uncapped silver nanoparticles have been prepared using less-explored DC arc thermal plasma technique by considering its large scale generation capability. It is observed that the resultant nanoparticles show size as well as optical property dependent antimicrobial effect.