Enhanced visible-light photocatalytic activity of N-doped C/Na2Ti6O13/TiO2 hollow spheres for efficient dye degradation.

Doping and hybridization with other semiconductors are highly effective ways to address the limitations, including their weak response to visible light and significant recombination of photogenerated carriers. In addition, the assisted carbon on the catalyst surface and the structural design have the advantage of being catalytically active. Herein, visible-light-active N-doped C/Na2Ti6O13/TiO2 hollow spheres (denoted as N-C/NTO/TiO2 HS) were successfully prepared using a facile two-step method and evaluated for methylene blue (MB) aqueous solution degradation under visible-light irradiation. The as-obtained N-C/NTO/TiO2 HS demonstrated improved photocatalytic efficiency (94 %) and pseudo-first-order kinetic degradation rate (0.023 min-1). Moreover, after three cycles of testing, N-C/NTO/TiO2 HS showed a 91 % degradation rate in its photostability. The enhanced photocatalytic performance was attributed to the combined effects of N-doping, carbon species on the surface, and the coupling of TiO2 and Na2Ti6O13 using morphology engineering. Finally, based on the experimental results, a possible photocatalytic mechanism was proposed. This study provides a rational approach toward the development of high-performance titanate-based photocatalysts for solar energy-assisted wastewater treatment.

Valorization of waste NiMH battery through recovery of critical rare earth metal: A simple recycling process for the circular economy.

The process flowsheet consists of three main circuits, i.e., metal extraction by acid leaching, critical rare earth metal (REM) recovery from leach liquor and pure Co/Ni recovery by solvent extraction. Quantitative metal extraction using 1 M H2SO4, pulp density of 25 g/L at 90 °C from waste NiMH battery was achieved. From leach liquor using 10 M NaOH, at pH 1.8, more than 99% REM was precipitated out and isolated through calcination at 600 °C. Undesired metals like Mn, Al, Zn, and Fe were scrubbed out from the leach liquor using 0. 7 M D2EPHA at the equilibrium pH of 2.30. From the scrubbed raffinate Co and Ni was separated using 0.5 M Cyanex 272 at pH 4.70 through solvent extraction. At pH 4.70 Co was completely extracted from solution leaving Ni in solution, which can be recovered completely. From Co loaded Cyanex 272, the Co was stripped by 1 M H2SO4 and regenerated Cyanex 272 can be reused and close the loop. Similarly, the undesired metal loaded D2EPHA can be regenerated and reused and close the loop. As the process is close-loop process recovers critical REMs, Co, and Ni, the valorization process efficiently addresses the circular economy and recycling challenges associated with waste NiMH battery.

Novel Carrier Doping Mechanism for Transparent Conductor: Electron Donation from Embedded Ag Nanoparticles to the Oxide Matrix.

A trade-off between the carrier concentration and carrier mobility is an inherent problem of traditional transparent conducting oxide (TCO) films. In this study, we demonstrate that the electron concentration of TCO films can be increased without deteriorating the carrier mobility by embedding Ag nanoparticles (NPs) into Al-doped ZnO (AZO) films. An increment of Ag NP content up to 0.7 vol % in the AZO causes the electron concentration rising to 4 × 1020 cm-3. A dependence of the conductivity on temperature suggests that the energy barrier for the electron donation from Ag NPs at room temperature is similar to the Schottky barrier height at the Ag-AZO interface. In spite of an increase in the electron concentration, embedded Ag NPs do not compromise the carrier mobility at room temperature. This is evidence showing that this electron donation mechanism by Ag NPs is different from impurity doping, which produces both electrons and ionized scattering centers. Instead, an increase in the Fermi energy level of the AZO matrix partially neutralizes Al impurities, and the carrier mobility of Ag NP embedded AZO film is slightly increased. The optical transmittance of mixture films with resistivity less than 1 × 10-3 Ω·cm still maintains above 85% in visible wavelengths. This opens a new paradigm to the design of alternative TCO composite materials which circumvent an inherent problem of the impurity doping.

Low-Temperature Modification of ZnO Nanoparticles Film for Electron-Transport Layers in Perovskite Solar Cells.

An electron-transport layer (ETL) that selectively collects photogenerated electrons is an important constituent of halide perovskite solar cells (PSCs). Although TiO2 films are widely used as ETL of PSCs, the processing of TiO2 films with high electron mobility requires high-temperature annealing and TiO2 dissociates the perovskite layer through a photocatalytic reaction. Here, we report an effective surface-modification method of a room-temperature processed ZnO nanoparticles (NPs) layer as an alternative to the TiO2 ETL. A combination of simple UV exposure and nitric acid treatment effectively removes the hydroxyl group and passivates surface defects in ZnO NPs. The surface modification of ZnO NPs increases the power conversion efficiency (PCE) of PSCs to 14 % and decreases the aging of PSCs under light soaking. These results suggest that the surface-modified ZnO film can be a good ETL of PSCs and provide a path toward low-temperature processing of efficient and stable PSCs that are compatible with flexible electronics.

Preparation of cobalt nanoparticles from polymorphic bacterial templates: A novel platform for biocatalysis.

Nanoparticles have gathered significant research attention as materials for enzyme immobilization due to their advantageous properties such as low diffusion rates, ease of manipulation, and large surface areas. Here, polymorphic cobalt nanoparticles of varied sizes and shapes were prepared using Micrococcus lylae, Bacillus subtilis, Escherichia coli, Paracoccus sp., and Haloarcula vallismortis as bacterial templates. Furthermore, nine lipases/carboxylesterases were successfully immobilized on these cobalt nanoparticles. Especially, immobilized forms of Est-Y29, LmH, and Sm23 were characterized in more detail for potential industrial applications. Immobilization of enzymes onto cobalt oxide nanoparticles prepared from polymorphic bacterial templates may have potential for efficient hydrolysis on an industrial-scale, with several advantages such as high retention of enzymatic activity, increased stability, and strong reusability.

Biomineralized multifunctional magnetite/carbon microspheres for applications in Li-ion batteries and water treatment.

Advanced functional materials incorporating well-defined multiscale architectures are a key focus for multiple nanotechnological applications. However, strategies for developing such materials, including nanostructuring, nano-/microcombination, hybridization, and so on, are still being developed. Here, we report a facile, scalable biomineralization process in which Micrococcus lylae bacteria are used as soft templates to synthesize 3D hierarchically structured magnetite (Fe3O4) microspheres for use as Li-ion battery anode materials and in water treatment applications. Self-assembled Fe3O4 microspheres with flower-like morphologies are systematically fabricated from biomineralized 2D FeO(OH) nanoflakes at room temperature and are subsequently subjected to post-annealing at 400 °C. In particular, because of their mesoporous properties with a hollow interior and the improved electrical conductivity resulting from the carbonized bacterial templates, the Fe3 O4 microspheres obtained by calcining the FeO(OH) in Ar exhibit enhanced cycle stability and rate capability as Li-ion battery anodes, as well as superior adsorption of organic pollutants and toxic heavy metals.

Germanium microflower-on-nanostem as a high-performance lithium ion battery electrode.

We demonstrate a new design of Ge-based electrodes comprising three-dimensional (3-D) spherical microflowers containing crystalline nanorod networks on sturdy 1-D nanostems directly grown on a metallic current collector by facile thermal evaporation. The Ge nanorod networks were observed to self-replicate their tetrahedron structures and form a diamond cubic lattice-like inner network. After etching and subsequent carbon coating, the treated Ge nanostructures provide good electrical conductivity and are resistant to gradual deterioration, resulting in superior electrochemical performance as anode materials for LIBs, with a charge capacity retention of 96% after 100 cycles and a high specific capacity of 1360 mA h g(-1) at 1 C and a high-rate capability with reversible capacities of 1080 and 850 mA h g(-1) at the rates of 5 and 10 C, respectively. The improved electrochemical performance can be attributed to the fast electron transport and good strain accommodation of the carbon-filled Ge microflower-on-nanostem hybrid electrode.

Adsorption of microbial esterases on Bacillus subtilis-templated cobalt oxide nanoparticles.

Due to low diffusion rates and large surface areas, nanomaterials have received great interest as supporting materials for enzyme immobilization. Here, the preparation of a cobalt oxide nanoparticle using Bacillus subtilis as a biological template and use of the nanostructure for microbial esterase immobilization is described. Morphological features and size distributions were investigated using electron microscopy (EM) and dynamic light scattering (DLS). Catalytic properties of enzyme-coated nanostructures were investigated using 4-methylumbelliferyl acetate and p-nitrophenyl (PNP) acetate as model substrates. Enzyme-coated nanostructures were observed to retain ∼85% of the initial activity after 15 successive reaction cycles, and enzyme immobilization processes could be repeated four times without a loss of immobilization potential. The present work demonstrates that B. subtilis-templated cobalt oxide nanoparticles have the potential to be used as biocompatible immobilization materials, and are promising candidates for the preparation of effective nanobiocatalysts.

Comparison of toxicity of different nanorod-type TiO2 polymorphs in vivo and in vitro.

It is predicted that the toxicity of nanoparticles may be different depending on the properties of the nanoparticles and biological system being tested. However, the factors that influence the toxicity of nanoparticles have not been adequately investigated. In this study, we characterized two types of TiO2 nanorods, anatase (ATO) and brookite (BTO), and compared their toxicity in vivo and in vitro. ATO and BTO differed from each other most notably in their surface areas. Treatment with the two TiO2 nanorods (10 µg ml(-1) ) produced similar effects on the cell cycle in eight cell lines which are derived from potential target organs of nanoparticles, with the BTO eliciting stronger responses than ATO in all cell lines, among the cell lines, H9C2 showed the maximal change. Similarly, when mice were exposed to two TiO2 nanorods (1 mg kg(-1) ), BTO induced clearer histopathological lesions and triggered a more robust secretion of inflammatory cytokines than ATO. Furthermore, we compared the cellular response of both TiO2 nanorods using BEAS-2B cells, the human bronchial epithelial cell line. Both nanorods induced cell death by increasing the formation of autophagosome-like vacuoles. The mitochondrial calcium concentration decreased by exposure of both types, but the distribution of lysosome and endoplasmic reticulum (ER) showed a clear difference between the two nanorods. Thus, we conclude that the surface area acts as an important factor which depends on toxicity of nanorod type-TiO2 nanoparticles. Furthermore, the toxicity of nanoparticles varies according to the type of cells tested, and that the assembly of autophagosome-like vacuoles is a critical part of the cellular response to nanoparticle exposure.

Highly reversible Li storage in hybrid NiO/Ni/graphene nanocomposites prepared by an electrical wire explosion process.

NiO/Ni/graphene nanocomposites were prepared using a simple and environmentally friendly method comprising an electrical wire pulse technique in oleic acid containing graphenes and subsequent annealing to form anodes for Li ion batteries. The control product of NiO/Ni nanocomposite was prepared under the same conditions and characterized by structural and electrochemical analysis. The obtained NiO/Ni/graphene nanocomposite particles had sizes of 5-12 nm and a high surface area of 137 m(2) g(-1). In comparison to NiO/Ni, NiO/Ni/graphene exhibited improved cycling performance and good rate capability. Reversible capacity was maintained at over 600 mA h g(-1) at 0.2 C and was attributed to the alleviation in volume change and improved electrical conductivity of NiO/Ni/graphene nanocomposites.

Hydrothermal realization of a hierarchical, flowerlike MnWO4@MWCNTs nanocomposite with enhanced reversible Li storage as a new anode material.

A phase-pure MnWO4-based nanocomposite, MnWO4@MWCNTs (MWCNTs=multiwalled carbon nanotubes), was successfully synthesized through a simple hydrothermal reaction at 180 °C by adjusting the pH of the precursor medium. The resulting nanocomposite maintains the original flowerlike morphology of MnWO4 with hierarchical structures composed of numerous single-crystalline nanorods that drive growth preferentially along the [001] direction. The growth mechanism for the flowerlike formations is also discussed. In addition, the Li electroactivity of pure MnWO4 and MnWO4@MWCNTs electrodes was investigated. As an anode for Li-ion batteries, the MnWO4@MWCNTs nanocomposite showed enhanced electrochemical performance in reversible Li storage relative to that shown by bare MnWO4 electrodes, including a high capacity of 425 mAh g(-1) and superior rate performance. This performance can be attributed to the synergistic effect of the nanocomposite combined with the MWCNTs, which provide efficient electron transport in their role as a conductor.

Scalable one-pot bacteria-templating synthesis route toward hierarchical, porous-Co3O4 superstructures for supercapacitor electrodes.

Template-driven strategy has been widely used to synthesize inorganic nano/micro materials. Here, we used a bottom-up controlled synthesis route to develop a powerful solution-based method of fabricating three-dimensional (3D), hierarchical, porous-Co3O4 superstructures that exhibit the morphology of flower-like microspheres (hereafter, RT-Co3O4). The gram-scale RT-Co3O4 was facilely prepared using one-pot synthesis with bacterial templating at room temperature. Large-surface-area RT-Co3O4 also has a noticeable pseudocapacitive performance because of its high mass loading per area (~10 mg cm(-2)), indicating a high capacitance of 214 F g(-1) (2.04 F cm(-2)) at 2 A g(-1) (19.02 mA cm(-2)), a Coulombic efficiency averaging over 95%, and an excellent cycling stability that shows a capacitance retention of about 95% after 4,000 cycles.

Comparison of toxicity between the different-type TiO2 nanowires in vivo and in vitro.

In this study, we compared their toxicity in vivo and in vitro based on the physicochemical properties of three different types of TiO2 nanowires, H2Ti3O7 nanowires (1HTO), hydrothermal treatment (2HTO), and calcination (3HTO) of 1HTO. The surface of 1HTO was smooth, and the surface of 2HTO was much rougher. The negative charge on the surface increased in the order of 2HTO, 3HTO, and 1HTO, whereas the surface area increased in the order of 3HTO, 1HTO, and 2HTO. The lung is a main exposure route of nanoparticles. On day 28 after a single instillation (1 mg/kg), three nanowires induced a Th2-type inflammatory response together with the relative increase in CD4⁺ T cells, especially by 2HTO. In vitro, three TiO2 nanowires (10 µg/ml) commonly induced the generation of cell debris in eight cell lines which may be the potential target organ of nanoparticles, especially by 2HTO. It seemed that the generation of cell debris coincides with the increase in autophagosome-like vacuoles in the cytosol. In further study using BEAS-2B cells originated from the lung, the protein amount from cells exposed to 2HTO decreased more clearly although the generation of reactive oxygen species (ROS) was less compared to 1HTO and 3HTO. Based on these results, we suggest that surface area may act as an important factor depends on the biological response by TiO2 nanowires. Furthermore, the increase in autophagosome-like vacuoles may be an important cause of cell death by nanoparticles with ROS.

Superior long-term cycling stability of SnO2 nanoparticle/multiwalled carbon nanotube heterostructured electrodes for Li-ion rechargeable batteries.

We demonstrate the fabrication of hybrid nanocomposite electrodes with a combination of SnO(2) nanoparticles (NPs) and conducting multiwalled carbon nanotube (MWCNT) anodes (SnO(2)@CNT) through the direct anchoring of SnO(2) NPs on the surface of electrophoretically pre-deposited MWCNT (EPD-CNT) networks via a metal-organic chemical vapor deposition process. This SnO(2)@CNT nanocomposite displays large reversible capacities of over 780, 510, and 470 mA h g(-1) at 1 C after 100, 500, and 1000 cycles, respectively. This outstanding long-term cycling stability is a result of the uniform distribution of SnO(2) NPs (~8.5 nm), a nanoscale EPD-CNT network with good electrical conductivity, and the creation of open spaces that buffer a large volume change during the Li-alloying/dealloying reaction of SnO(2).

Biomineralized Sn-based multiphasic nanostructures for Li-ion battery electrodes.

A method for preparing multiphasic hollow rods consisting of nanoscale Sn-based materials through a thermochemical reduction process involving bacteria and Sn oxides is reported. This facile process involves the bacteria-mediated synthesis of SnO(2) nanoparticles that form on bacterial surfaces used as templates at room temperature. The subsequent template removal proceeds via a reduction of the heat-treated SnO(2) nanoparticles at 400 °C under reduction atmosphere, leaving free-standing hollow nanocomposite rods. These unique hollow nanocomposite rods have multiple components, including amorphous carbon, metal oxides (SnO(2) and SnO), and metallic Sn, and retain the original rod shapes. The systematic phase and morphological evolutions of the bacteria@SnO(2) composite rods are investigated by performing controlled thermochemical reduction at various temperatures. In addition, the application of multiphasic hollow nanocomposite rods as anode materials for rechargeable Li-ion batteries is evaluated. These materials exhibit excellent electrochemical performance, with capacities of about 505 and 350 mA h g(-1) at current densities of 157 and 392 mA g(-1), respectively.

Synthesis of core/shell spinel ferrite/carbon nanoparticles with enhanced cycling stability for lithium ion battery anodes.

Monodispersed core/shell spinel ferrite/carbon nanoparticles are formed by thermolysis of metal (Fe3+, Co2+) oleates followed by carbon coating. The phase and morphology of nanoparticles are characterized by x-ray diffraction and transmission electron microscopy. Pure Fe3O4 and CoFe2O4 nanoparticles are initially prepared through thermal decomposition of metal­oleate precursors at 310 degrees C and they are found to exhibit poor electrochemical performance because of the easy aggregation of nanoparticles and the resulting increase in the interparticle contact resistance. In contrast, uniform carbon coating of Fe3O4 and CoFe2O4 nanoparticles by low-temperature (180 degrees C) decomposition of malic acid allowed each nanoparticle to be electrically wired to a current collector through a conducting percolative path. Core/shell Fe3O4/C and CoFe2O4/C nanocomposite electrodes show a high specific capacity that can exceed 700 mAh g(-1) after 200 cycles, along with enhanced cycling stability.

Electrochemical performance of NixCo1-xMoO4 (0 ≤ x ≤ 1) nanowire anodes for lithium-ion batteries.

NixCo1-xMoO4 (0 ≤ x ≤ 1) nanowire electrodes for lithium-ion rechargeable batteries have been synthesized via a hydrothermal method, followed by thermal post-annealing at 500°C for 2 h. The chemical composition of the nanowires was varied, and their morphological features and crystalline structures were characterized using field-emission scanning electron microscopy and X-ray powder diffraction. The reversible capacity of NiMoO4 and Ni0.75Co0.25MoO4 nanowire electrodes was larger (≈520 mA h/g after 20 cycles at a rate of 196 mA/g) than that of the other nanowires. This enhanced electrochemical performance of NixCo1-xMoO4 nanowires with high Ni content was ascribed to their larger surface area and efficient electron transport path facilitated by their one-dimensional nanostructure.

Fabrication of core/shell ZnWO4/carbon nanorods and their Li electroactivity.

Carbon-coated ZnWO4 [C-ZW] nanorods with a one-dimensional core/shell structure were synthesised using hydrothermally prepared ZnWO4 and malic acid as precursors. The effects of the carbon coating on the ZnWO4 nanorods are investigated by thermogravimetry, high-resolution transmission electron microscopy, and Raman spectroscopy. The coating layer was found to be in uniform thickness of approximately 3 nm. Moreover, the D and G bands of carbon were clearly observed at around 1,350 and 1,600 cm-1, respectively, in the Raman spectra of the C-ZW nanorods. Furthermore, lithium electroactivities of the C-ZW nanorods were evaluated using cyclic voltammetry and galvanostatic cycling. In particular, the formed C-ZW nanorods exhibited excellent electrochemical performances, with rate capabilities better than those of bare ZnWO4 nanorods at different current rates, as well as a coulombic efficiency exceeding 98%. The specific capacity of the C-ZW nanorods maintained itself at approximately 170 mAh g-1, even at a high current rate of 3 C, which is much higher than pure ZnWO4 nanorods.

Facile synthesis of nano-Li4 Ti5O12 for high-rate Li-ion battery anodes.

One of the most promising anode materials for Li-ion batteries, Li4Ti5O12, has attracted attention because it is a zero-strain Li insertion host having a stable insertion potential. In this study, we suggest two different synthetic processes to prepare Li4Ti5O12 using anatase TiO2 nanoprecursors. TiO2 powders, which have extraordinarily large surface areas of more than 250 m2 g-1, were initially prepared through the urea-forced hydrolysis/precipitation route below 100°C. For the synthesis of Li4Ti5O12, LiOH and Li2CO3 were added to TiO2 solutions prepared in water and ethanol media, respectively. The powders were subsequently dried and calcined at various temperatures. The phase and morphological transitions from TiO2 to Li4Ti5O12 were characterized using X-ray powder diffraction and transmission electron microscopy. The electrochemical performance of nanosized Li4Ti5O12 was evaluated in detail by cyclic voltammetry and galvanostatic cycling. Furthermore, the high-rate performance and long-term cycle stability of Li4Ti5O12 anodes for use in Li-ion batteries were discussed.

Synthesis of cuprous oxide nanocomposite electrodes by room-temperature chemical partial reduction.

We demonstrate a template-free synthetic approach for the preparation of a highly conductive Cu/Cu(2)O nanocomposite electrode by a chemical reduction process. Cu(2)O octahedra were prepared through chemical dehydrogenation of as-synthesized Cu(OH)(2) nanowire precursors. To provide a sufficiently electron-conducting network, the Cu(2)O particles were transformed into Cu/Cu(2)O nanocomposites by an intentional reduction process. The Cu/Cu(2)O nanocomposite electrodes showed enhanced cycling performance compared to Cu(2)O particles. Furthermore, their rate capabilities were superior to those of their mechanically mixed Cu/Cu(2)O counterparts. This enhanced electrochemical performance of the hybrid Cu/Cu(2)O nanocomposites was ascribed to the formation of homogeneous nanostructures, offering an efficient electron-transport path provided by the presence of highly dispersed Cu nanoparticles.