Carbon-coated ZnFe2O4 spheres with sizes of ~110–180 nm anchored on graphene nanosheets (ZF@C/G) are successfully prepared and applied as anode materials for lithium ion batteries (LIBs). The obtained ZF@C/G presents an initial discharge capacity of 1235 mAh g?1 and maintains a reversible capacity of 775 mAh g?1 after 150 cycles at a current density of 500 mA g?1. After being tested at 2 A g?1 for 700 cycles, the capacity still retains 617 mAh g?1. The enhanced electrochemical performances can be attributed to the synergetic role of graphene and uniform carbon coating (~3–6 nm), which can inhibit the volume expansion, prevent the pulverization/aggregation upon prolonged cycling, and facilitate the electron transfer between carbon-coated ZnFe2O4 spheres. The electrochemical results suggest that the synthesized ZF@C/G nanostructures are promising electrode materials for high-performance lithium ion batteries.
Solution combustion synthesis (SCS) is an effective and rapid method for synthesizing nanocrystalline materials. However, the control over size, morphology, and microstructure are rather limited in SCS. Here, we develop a novel ultrasonic-assisted solution combustion route to synthesize the porous and nano-sized Na3V2(PO4)3/C composites, and reveal the effects of ultrasound on the structural evolution of NVP/C. Due to the cavitation effects generated from ultrasonic irradiation, the ultrasonic-assisted SCS can produce honeycomb precursor, which can be further transformed into porous Na3V2(PO4)3/C with reticular and hollow structures after thermal treatment. When used as cathode material for Na-ion batteries, the porous Na3V2(PO4)3/C delivers an initial discharge capacity of 118 mAh g?1 at 0.1 C and an initial coulombic efficiency of 85%. It can retain 93.8% of the initial capacity after 120 cycles at 0.2 C. The results demonstrate that ultrasonic-assisted SCS can be a new strategy to design crystalline nanomaterials with tunable microstructures.
Graphical abstract Porous and nano-sized Na3V2(PO4)3/C composites with reticular and hollow structures are synthesized by an ultrasonic-assisted solution combustion route due to the cavitation effects, and exhibit excellent electrochemical performance as cathode in sodium ion battery.
In this study, the magnetically recyclable Fe3O4@C/BiOBr heterojunction with enhanced visible light-driven photocatalytic ability was obtained by two-step solvothermal method. The phase, morphology, and structure of the samples were investigated by XRD, FESEM, HRTEM, and XPS. The Fe3O4@C/BiOBr heterojunction was composed of Fe3O4@C sphere and BiOBr microsphere with diameters of 200 nm and 1000 nm, respectively. The photocatalytic performance of Fe3O4@C/BiOBr composite for RhB was examined under visible light irradiation. The photocatalytic activity of Fe3O4@C/BiOBr composite was much higher than that of pure BiOBr and Fe3O4@C. After 35 min of irradiation, 97% of RhB could be removed with the Fe3O4@C/BiOBr photocatalyst. Based on radical trapping experiments of active species, the mechanism of enhanced photocatalytic performance was proposed. In addition, the superparamagnetic property of the photocatalyst not only allows its easy recyclability by an external magnetic field but also maintains high photocatalytic activity after five cyclic experiments.
In this paper, an efficient strategy for the synthesis of graphene nanobelt-titanium dioxide/graphitic carbon nitride (graphene-TiO2/g-C3N4) heterostructure photocatalyst was applied to fabricate a kind of visible-light-driven photocatalyst. The heterostructure shows higher absorption edge towards harvesting more solar energy compared with pure TiO2 and pure g-C3N4 respectively. Furthermore, the as-prepared graphene-TiO2/g-C3N4 heterostructure can show enhanced photocatalytic activity under visible-light irradiation. These outstanding performances of photocatalytic activities for graphene-TiO2/g-C3N4 composites can be attributed to the heterojunction interfaces which can separate the electron-hole pairs and impede the recombination of electrons and holes more efficiently. This study conclusively demonstrates a facile and environmentally friendly new strategy to design highly efficient graphene-TiO2/g-C3N4 heterostructure photocatalytic materials for potential applications under visible-light irradiation.
One-dimensional Ce3+-doped Li4Ti5O12 (Li4Ti5?xCexO12, x?=?0, 0.01, 0.02, and 0.05) sub-microbelts with the width of approximately 500 nm and thickness of about 200 nm have been synthesized via the facile electrospinning method. The structure and morphology of the as-prepared samples are characterized by XRD, TEM, SEM, BET, HRTEM, XPS, and AFM. Importantly, one-dimensional Li4Ti5O12 sub-microbelts can be well preserved with the introduction of Ce3+ ions, while CeO2 impurity is obtained when x is greater than or equal to 0.02. The comparative experiments prove that Ce3+-doped Li4Ti5O12 electrodes exhibit the brilliant electrochemical performance than undoped counterpart. Particularly, the reversible capacity of Li4Ti4.98Ce0.02O12 electrode reaches up to 139.9 mAh g?1 and still maintains at 132.6 mAh g?1 even after 100 cycles under the current rate of 4 C. The superior lithium storage properties of Li4Ti4.98Ce0.02O12 electrode could be attributed to their intrinsic structure advantage as well as enhanced overall conductivity.
Ternary copper indium sulfide (CIS) nanocrystals (NCs) have been synthesized by mixing of binary precursor [CuI(bdpa)2][CuICl2] (1) and/or [CuI(mdpa)2][CuICl2] (2) (where, mdpa and bdpa represent methyl and benzyl ester of 3,5-dimethyl pyrazole-1-dithioic acid, respectively) with InCl3 in a low-temperature solvothermal process. The +1 oxidation state of copper and the atomic ratio Cu to S (1:2) is atomically maintained in the pyrazole-based Cu(I)–S precursor to synthesize phase pure CuInS2. Coordinating solvents like ethylene diamine (EN) and ethylene glycol (EG) have been used in the synthesis without any surfactants. No use of external surfactants in the synthesis of CIS nanoparticles reveals that precursor acts as stabilizing agent. The synthesized nanocrystals were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDX) studies. The optical property of the nanocrystals shows a pronounced quantum confinement effect in the particles with band gap energy ca. 1.5 eV. The formation mechanism of ternary CIS has been proposed. The pore size distributions of the particles show the average pore diameters 13.1 nm from 1 and 5.3 nm from 2. The calculated values of the specific surface area are 8.123 and 9.577 m2/g for 1 and 2, respectively. The excellent photocatalytic degradation of rose bengal (RB) and rhodamine B (RhB) was demonstrated by the porous CIS nanocrystals.
Graphical abstract Enhanced photocatalytic activity of ternary CuInS2 nanocrystals synthesized from the combination of a binary Cu(I)S precursor and InCl3. Gopinath Mondal, Ananyakumari Santra, Sumanta Jana, Nimai Chand Pramanik, Anup Mondal and Pulakesh Bera
Previous studies on the fate of engineered nanoparticles (ENPs) incorporated in paints mainly focused on the release of the particles as affected by a limited number of factors or monitoring their release from natural sources. In this study, the effects of four factors (i.e., weathering duration, water pH, rainfall duration and intensity) were investigated on the release of SiO2-ENPs, Ag-ENPs, and TiO2-ENPs from paints applied on panels. The static water immersion test showed that the concentrations of studied particles all increased with weathering duration. At low and high pH, SiO2-ENPs and Ag-ENPs showed a higher release, while the release of TiO2-ENPs was relatively high at low pH. With increased simulated rainfall duration, the concentration released decreased for Si, and the opposite was observed for Ag, while no obvious correlation was noted for Ti. With greater rainfall intensity, there was increasing release of all particles. In total, the releases of Ag-ENPs and TiO2-ENPs were extremely low and within the level of 21.32–42.16 μg L?1and 0.6–2.3 μg L?1, respectively, while the values for SiO2-ENPs were in the range of 7.5–12 mg L?1. Additionally, microscopic results highlighted that SiO2-ENPs were mainly released in the form of agglomerates, and only a small fraction was below 0.1 μm. Considering these influence factors together, conclusions may be made that weathering time and rainfall duration are more important in controlling release than water pH.
CeO2 and Fe2O3 co-modified titanate nanosheet (Fe2O3/CeO2@TNS) was prepared by one-pot hydrothermal method; the photocatalyst exhibited large surface area with CeO2 and Fe2O3 particles well dispersed on the surface. The results of XRD, BET, and Raman proved that the CeO2 and Fe2O3 introduced in the TNS influenced its structure evolution from 3D to 2D. The modification resulted in a shift of the absorption edge toward a longer wavelength and the band gap reduced to 2.87 eV. The three-component systems performed excellent photocatalytic activity and cycle stability on phenol and methyl blue (MB) solution under sunlight; nearly total phenol and MB were degraded in dozens of minutes. And the reaction rate constant (K) of Fe2O3/CeO2@TNS on phenol degradation was 1.77, 3.25, 4.88, and 13-fold of Fe2O3@TNS, CeO2@TNS, bare TNS, and P25, respectively. The enhanced photocatalytic activity could be ascribed to the efficient separation of photogenerated pairs through the formation of tandem n-n-n heterojunction among the three-component systems. This work will be useful for the design of other tandem n-n-n heterojunction photocatalytic systems for application in energy conversion and environmental remediation.
Metal nanoparticles have been combined with magnet metal–organic frameworks (MOFs) to afford new materials that demonstrate an efficient catalytic degradation, high stability, and excellent reusability in areas of catalysis because of their exceptionally high surface areas and structural diversity. Magnetic MxOy@N-C (M = Fe, Co, Mn) nanocrystals were formed on nitrogen-doped carbon surface by using 8-hydroxyquinoline as a C/N precursor. The Co@N-C, MnO@N-C, and Fe/Fe2O3@N-C catalysts were characterized by X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), N2 adsorption/desorption, and X-ray photoelectron spectroscopy (XPS). The catalytic performances of catalysts were thoroughly investigated in the oxidation of aniline solution based on sulfate radicals (SO4?.) toward Fenton-like reaction. Magnetic MxOy@N-C exhibits an unexpectedly high catalytic activity in the degradation of aniline in water. A high magnetic MxOy@N-C catalytic activity was observed after the evaluation by aniline degradation in water. Aniline degradation was found to follow the first-order kinetics, and as a result, various metals significantly affected the structures and performances of the catalysts, and their catalytic activity followed the order of Co > Mn > Fe. The nanoparticles displayed good magnetic separation under the magnetic field.
Novel feather duster-like nickel sulfide (NiS) @ molybdenum sulfide (MoS2) with hierarchical array structure is synthesized via a simple one-step hydrothermal method, in which a major structure of rod-like NiS in the center and a secondary structure of MoS2 nanosheets with a thickness of about 15–55 nm on the surface. The feather duster-like NiS@MoS2 is employed as the counter electrode (CE) material for the dye-sensitized solar cell (DSSC), which exhibits superior electrocatalytic activity due to its feather duster-like hierarchical array structure can not only support the fast electron transfer and electrolyte diffusion channels, but also can provide high specific surface area (238.19 m2 g?1) with abundant active catalytic sites and large electron injection efficiency from CE to electrolyte. The DSSC based on the NiS@MoS2 CE achieves a competitive photoelectric conversion efficiency of 8.58%, which is higher than that of the NiS (7.13%), MoS2 (7.33%), and Pt (8.16%) CEs under the same conditions.
Graphical abstract Novel feather duster-like NiS@MoS2 hierarchical structure array with superior electrocatalytic activity was fabricated by a simple one-step hydrothermal method.
Carbon materials have attracted great attention in CO2 capture and energy storage due to their excellent characteristics such as tunable pore structure, modulated surface properties and superior bulk conductivities, etc. Biomass, provided by nature with non-toxic, widespread, abundant, and sustainable advantages, is considered to be a very promising precursor of carbons for the view of economic, environmental, and societal issues. However, the preparation of high-performance biomass-derived carbons is still a big challenge because of the multistep process for their synthesis and subsequent activation. Herein, hierarchically porous structured carbon materials have been prepared by directly carbonizing dried cauliflowers without any addition of agents and activation process, featuring with large specific surface area, hierarchically porous structure and improved pore volume, as well as suitable nitrogen content. Being used as a solid-state CO2 adsorbent, the obtained product exhibited a high CO2 adsorption capacity of 3.1 mmol g?1 under 1 bar and 25 °C and a remarkable reusability of 96.7% retention after 20 adsorption/regeneration cycles. Our study reveals that choosing a good biomass source was significant as the unique structure of precursor endows the carbonized product with abundant pores without the need of any post-treatment. Used as an electrode material in electrochemical capacitor, the non-activated porous carbon displayed a fairly high specific capacitance of 228.9 F g?1 at 0.5 A g?1 and an outstanding stability of 99.2% retention after 5000 cycles at 5 A g?1.
Graphical abstract Hierarchically porous structured carbon materials are prepared by directly carbonizing dried cauliflower without any agents and process of activation for high performance of CO2 capture and capacitor.
In flame spray pyrolysis (FSP), the generation of uniform nanoparticles can be quite challenging due to difficulties in controlling droplet sizes during liquid spraying and uneven flame temperature. Here, we report a method to produce relatively uniform nanocrystals of a Tb3+ doped Y2O3 phosphor. In ethanol, metal nitrate precursors were simply mixed with organic surfactants to form a homogeneous solution which was then subjected to FSP. Depending on relative concentrations of the surfactant (oleic acid) to the metal precursors (yttrium and terbium nitrates), different sizes and morphologies of Y2O3:Tb3+ particles were obtained. By adjusting the surfactant concentration, Y2O3:Tb3+ crystals as small as 20~25 nm were acquired. X-ray diffraction and transmittance electron microscopy were used to prove that as-synthesized nanoparticles were highly crystalline due to the high temperature of FSP. X-ray photoelectron spectroscopy revealed that terbium dopants were well distributed throughout Y2O3 particles and a small portion of carbonate impurities were remained on the surface of particles, presumably originated from incomplete combustion of the organic surfactants. Photoluminescence (PL) spectra of Y2O3:Tb3+ nanocrystals exhibited a green light emission ensuring that the terbium doping was successfully occurred. However, when post-annealing was performed on the nanocrystals, their PL was dramatically enhanced indicating that quenching centers such as carbonate impurities and surface defects may have been removed by the annealing process. Owing to the continuous processability of FSP, this current method can be a practical way to produce nanoparticles in a large quantity. The obtained Y2O3:Tb3+ nanocrystals were used to fabricate a transparent film with poly-ethylene-co-vinyl acetate (poly-EVA) polymer, which was suitable for a spectral converting layer for a solar cell.
The Br-doped hollow TiO2 photocatalysts were prepared by a simple hydrothermal process on the carbon sphere template following with calcination at 400 °C. The structure and properties of photocatalysts were characterized by X-ray diffraction, Raman spectrum, scanning electron microscope, transmission electron microscopy, N2 desorption–adsorption, UV–Vis spectroscopy, and X-ray photoelectron spectroscopy. The TiO2 hollow spheres are in diameter of 500 nm with shell thickness of 50 nm. The shell is composed of small anatase nanoparticles with size of about 10 nm. The TiO2 hollow spheres exhibit high crystalline and high surface area of 89.208 m2/g. With increasing content of Br doping, the band gap of TiO2 hollow spheres decreased from 2.85 to 1.75 eV. The formation of impurity band in the band gap would narrow the band gap and result in the red shift of absorption edge from 395 to 517 nm, which further enhances the photocatalytic activity. The appropriate Br doping improves the photocatlytic activity significantly. The TiO2 hollow spheres with 1.55% Br doping (0.5Br-TiO2) exhibit the highest photocatalytic activity under full light. More than 98% of RhB, MO, and MB can be photodegraded using 0.5Br-TiO2 with concentration of 10 mg/L in 40, 30, and 30 min, respectively. The degradation rate of Br-doped photocatalysts was 40% faster than undoped ones.
Water dispersible boron nanoparticles have great potential as materials for boron neutron capture therapy of cancer and magnetic resonance imaging, if they are prepared on a large scale with uniform size and shape and hydrophilic modifiable surface. We report the first method to prepare spherical, monodisperse, water dispersible boron core silica shell nanoparticles (B@SiO2 NPs) suitable for aforementioned biomedical applications. In this method, 40 nm elemental boron nanoparticles, easily prepared by mechanical milling and carrying 10-undecenoic acid surface ligands, are hydrosilylated using triethoxysilane, followed by base-catalyzed hydrolysis of tetraethoxysilane, which forms a 10-nm silica shell around the boron core. This simple two-step process converts irregularly shaped hydrophobic boron particles into the spherically shaped uniform nanoparticles. The B@SiO2 NPs are dispersible in water and the silica shell surface can be modified with primary amines that allow for the attachment of a fluorophore and, potentially, of targeting moieties.
Mo-doped V2O5 hierarchical nanorod/nanoparticle core/shell porous microspheres (MVHPMs) were prepared via a simple hydrothermal approach using ammonium metavanadate and ammonium molybdate as precursors followed by a thermal annealing process. The samples were characterized by XRD, SEM, TEM, EDS, and XPS carefully; it confirmed that porous microspheres with uniform Mo doping in the V2O5 matrix were obtained, and it contains an inner core self-assembled with 1D nanorods and outer shell consisting of nanoparticles. A plausible growth mechanism of Mo-doped V2O5 (Mo-V2O5) porous microspheres is suggested. The unique microstructure made the Mo-V2O5 hierarchical microspheres a good cathode material for Li-ion battery. The results indicate the synthesized Mo-V2O5 hierarchical microspheres exhibit well-improved electrochemical performance compared to the undoped samples. It delivers a high initial reversible capacity of 282 mAh g?1 at 0.2 C, 208 mAh g?1 at 2 C, and 111 mAh g?1 at 10 C, and it also exhibits good cycling stabilities; a capacity of 144 mAh g?1 is obtained after 200 cycles at 6 C with a capacity retention of >?82%, which is much high than that of pure V2O5 (95 mAh g?1 with a capacity retention of 72%).
A facile and efficient one-pot method for the synthesis of well-dispersed hollow CuFe2O4 nanoparticles (H-CuFe2O4 NPs) in the presence of cellulose nanocrystals (CNC) as the support was described. Based on the one-pot solvothermal condition control, magnetic H-CuFe2O4 NPs were in-situ grown on the CNC surface uniformly. TEM images indicated good dispersity of H-CuFe2O4 NPs with uniform size of 300 nm. The catalytic activity of H-CuFe2O4/CNC was tested in the catalytic reduction of 4-nitrophenol (4-NP) in aqueous solution. Compared with most CNC-based ferrite catalysts, H-CuFe2O4/CNC catalyst exhibited an excellent catalytic activity toward the reduction of 4-NP. The catalytic performance of H-CuFe2O4/CNC catalyst was remarkably enhanced with the rate constant of 3.24 s?1 g?1, which was higher than H-CuFe2O4 NPs (0.50 s?1 g?1). The high catalytic activity was attributed to the introduction of CNC and the special hollow mesostructure of H-CuFe2O4 NPs. In addition, the H-CuFe2O4/CNC catalyst promised good conversion efficiency without significant decrease even after 10 cycles, confirming relatively high stability. Because of its environmental sustainability and magnetic separability, H-CuFe2O4/CNC catalyst was shown to indicate that the ferrite nanoparticles supported on CNC were acted as a promising catalyst and exhibited potential applications in numerous ferrite based catalytic reactions.
Sm3+-doped SrSnO3 (SrSnO3:Sm3+) nanopowders were synthesized by a simple hydrothermal method and followed by a heat treatment process. The as-synthesized nanopowders were assembled in dye-sensitized solar cells (DSSCs) to investigate their photoelectric properties. X-ray diffraction (XRD), scanning electron microscope (SEM), and energy-dispersive spectrometer (EDS) confirmed the formation of SrSnO3:Sm3+ nanopowders with perovskite structure. The ultraviolet-visible absorption spectra and photoluminescence spectra indicate a down-conversion from ultraviolet light to visible light which matches the strong absorption region of the N719 dye. The DSSC based on SrSnO3:Sm3+ photo-anode improved its photoelectric conversion efficiency (η) via the down-conversion of doped Sm3+. Under the irradiation of the simulated sunlight with 100 mW/cm2, the DSSC based on SrSnO3 doping with Sm3+ of 0.6 wt% showed the highest η of 1.54%, which improved 71.11% compared with the DSSC based on pure SrSnO3.
Addition reaction between C60 and ethylenediamine occurred at room temperature in an ambient condition. C60-ethylenediamine adduct particles were prepared by mixing toluene solutions of C60 and ethyelenediamine. Average diameter of the C60-ethylenediamine adduct particles was changed non-linearly according to the reaction time, which were observed using transmission electron microscopy. Early stage of the reaction, the diameter of the adduct particles was changed from about 250 to about 430 nm. Then, the size of the adduct particles was converged to about 300 nm. During this addition reaction, the crystalline sizes of adduct particles were constant about 2–3 nm, regardless of the sizes of the adduct particles, which were determined by X-ray diffraction measurement.
In this study Pt, Re, and SnO2 nanoparticles (NPs) were combined in a controlled manner into binary and ternary combinations for a possible application for ethanol oxidation. For this purpose, zeta potentials as a function of the pH of the individual NPs solutions were measured. In order to successfully combine the NPs into Pt/SnO2 and Re/SnO2 NPs, the solutions were mixed together at a pH guaranteeing opposite zeta potentials of the metal and oxide NPs. The individually synthesized NPs and their binary/ternary combinations were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) analysis. FTIR and XPS spectroscopy showed that the individually synthesized Pt and Re NPs are metallic and the Sn component was oxidized to SnO2. STEM showed that all NPs are well crystallized and the sizes of the Pt, Re, and SnO2 NPs were 2.2, 1.0, and 3.4 nm, respectively. Moreover, EDS analysis confirmed the successful formation of binary Pt/SnO2 and Re/SnO2 NP, as well as ternary Pt/Re/SnO2 NP combinations. This study shows that by controlling the zeta potential of individual metal and oxide NPs, it is possible to assemble them into binary and ternary combinations.
A novel approach has been made to tailor Niobium pentoxide (Nb2O5) as a coating material on the surface of lithium iron phosphate (LiFePO4) via a facile polyol technique. The coating content was optimized at 1 wt%. The superficial coating demonstrated superior discharge capacity than the pristine LiFePO4. However, increasing the coating content further would result in a capacity loss. This may be due to the electrochemical inactiveness that increases with the content of the coating material, and 1 wt% of Nb2O5-coated LiFePO4 sample exhibits initial discharge capacity of 163 mAh g?1 at a current of 0.1 C and retains a stable discharge capacity of 143 mAh g?1 up to 400 cycles at 1 C rate with a coulombic efficiency of 98%.
