Cationic and anionic cross-assisted synergistic photocatalytic removal of binary organic dye mixture using Ni-doped perovskite oxide.

Organic dyes present in industrial wastewater are the major contributor to water pollution, which harm human health and the environment. Photocatalytic dye degradation is an effective strategy for water remediation by converting these organic dyes waste into non-harmful by-products. Therefore, in this study, Ni-doped LaFeO3 (NLFO) perovskite nanoparticles were extensively explored for photocatalytic degradation of cationic and anionic dyes and their mixture. The NLFO nanoparticles were successfully synthesized by surfactant assisted hydrothermal method under controlled Ni doping. The X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM) revealed the variation in size (40-70 nm) of orthorhombic crystalline LFO nanoparticles with Ni doping and hence the size of microspheres (0.78. to 1.78 µm). The kinetic studies revealed that the LaFe0·6Ni0·4O3 performed well by providing degradation efficiency of 99.2% in 210 min, 99.1% in 100 min, and 98.4% in 70 min for Crystal Violet (CV), Congo Red (CR), and their mixture with rate constant of 0.019, 0.039, and 0.055 min-1 respectively. The radical scavenger tests indicated the synergetic contributions of O2- and •OH- active radicals in faster degradation of CV and CR dye mixture. The stepwise fragmentation of dye molecule during the photocatalytic degradation identified from the LCMS indicates the degradation of CV dye through de-alkylation and benzene ring breaking, whereas azo bond cleavage and oxidation lead to low molecular weight intermediates for CR dye, which all together helped to degrade their dye mixture (50 mg L-1 and 100 mg L-1) in significantly lesser time (70 min). Overall, the Ni-doped LFO microsphere consisting of nanoparticles acts as a superior catalyst for the more efficient and faster degradation of binary dye mixture.

Porous nanorods by stacked NiO nanoparticulate exhibiting corn-like structure for sustainable environmental and energy applications.

A porous 1D nanostructure provides much shorter electron transport pathways, thereby helping to improve the life cycle of the device and overcome poor ionic and electronic conductivity, interfacial impedance between electrode-electrolyte interface, and low volumetric energy density. In view of this, we report on the feasibility of 1D porous NiO nanorods comprising interlocked NiO nanoparticles as an active electrode for capturing greenhouse CO2, effective supercapacitors, and efficient electrocatalytic water-splitting applications. The nanorods with a size less than 100 nm were formed by stacking cubic crystalline NiO nanoparticles with dimensions less than 10 nm, providing the necessary porosity. The existence of Ni2+ and its octahedral coordination with O2- is corroborated by XPS and EXAFS. The SAXS profile and BET analysis showed 84.731 m2 g-1 surface area for the porous NiO nanorods. The NiO nanorods provided significant surface-area and the active-surface-sites thus yielded a CO2 uptake of 63 mmol g-1 at 273 K via physisorption, a specific-capacitance (CS) of 368 F g-1, along with a retention of 76.84% after 2500 cycles, and worthy electrocatalytic water splitting with an overpotential of 345 and 441 mV for HER and OER activities, respectively. Therefore, the porous 1D NiO as an active electrode shows multifunctionality toward sustainable environmental and energy applications.

Photocatalytic activity of MnTiO3 perovskite nanodiscs for the removal of organic pollutants.

MTO nanodiscs synthesized using the hydrothermal approach were explored for the photocatalytic removal of methylene blue (MB), rhodamine B (RhB), congo red (CR), and methyl orange (MO). The disc-like structures of ~16 nm thick and ~291 nm average diameter of stoichiometric MTO were rhombohedral in nature. The MTO nanodiscs delivered stable and recyclable photocatalytic activity under Xe lamp irradiation. The kinetic studies showed the 89.7, 80.4, 79.4, and 79.4 % degradation of MB, RhB, MO, and CR at the rate constants of 0.011(±0.001), 0.006(±0.001), 0.007(±0.0007), and 0.009 (±0.0001) min-1, respectively, after the 180 min of irradiation. The substantial function of photogenerated holes and hydroxide radicals pertaining to the dye removal phenomena is confirmed by radical scavenger trapping studies. Overall, the present studies provide a way to develop pristine and heterostructure perovskite for photocatalysts degradation of various organic wastes.

Eco-Friendly Synthesis, Crystal Chemistry, and Magnetic Properties of Manganese-Substituted CoFe2O4 Nanoparticles.

The authors report on the effect of manganese (Mn) substitution on the crystal chemistry, morphology, particle size distribution characteristics, chemical bonding, structure, and magnetic properties of cobalt ferrite (CoFe2O4) nanoparticles (NPs) synthesized by a simple, cost-effective, and eco-friendly one-pot aqueous hydrothermal method. Crystal structure analyses indicate that the Mn(II)-substituted cobalt ferrites, Co1-x Mn x Fe2O4 (CMFO, x = 0.0-0.5), were crystalline with a cubic inverse spinel structure (space group Fd 3 m ). The average crystallite size increases from 8 to 14 nm with increasing Mn(II) content; the crystal growth follows an exponential growth function while the lattice parameters follow Vegard's law. Chemical bonding analyses made using Raman spectroscopic studies further confirm the cubic inverse spinel phase. The relative changes in specific vibrational modes related to octahedral sites as a function of Mn content suggest a gradual change of measure of inversion of the ferrite lattice at nanoscale dimensions. Small-angle X-ray scattering and electron microscopy revealed a narrow particle size distribution with the spherical shape morphology of the CMFO NPs. The zero-field-cooled and field-cooled magnetic measurements revealed the superparamagnetic behavior of CMFO NPs at room temperature. The sample with x = 0.3 indicates a lower value of blocking temperature (9.16 K) with the improved (maximum) value of saturation magnetization. The results and the structure-composition-property correlation suggest that the economic, eco-friendly hydrothermal approach can be adopted to process superparamagnetic nanostructured magnetic materials at a relatively lower temperature for practical electronic and electromagnetic device applications.

Structural correlation of a nanoparticle-embedded mesoporous CoTiO3 perovskite for an efficient electrochemical supercapacitor.

We synthesized mesoporous cobalt titanate (CTO) microrods via the sol-gel method as an outstanding working electrode for the supercapacitor. The mesoporous CTO microrods were amassed in hexagonal shapes of an average width of ∼670 nm, and were composed of nanoparticles of average diameter ∼41 nm. The well crystalline CTO microrods of the hexagonal phase to the R3̄ space group possessed an average pore size distribution of 3.92 nm throughout the microrod. The mesoporous CTO microrods with increased textural boundaries played a vital role in the diffusion of ions, and they provided a specific capacitance of 608.4 F g-1 and a specific power of 4835.7 W kg-1 and a specific energy of 9.77 W h kg-1 in an aqueous 2 M KOH electrolyte, which was remarkably better than those of Ti, La, Cr, Fe, Ni, and Sr-based perovskites or their mixed heterostructures supplemented by metal oxides as an impurity. Furthermore, the diffusion-controlled access to the OH- ions (0.27 µs) deep inside the microrod conveyed high stability, a long life cycle for up to 1950 continuous charging-discharging cycles, and excellent capacitance retention of 82.3%. Overall, the mesoporous CTO shows its potential as an electrode for a long-cycle supercapacitor, and provides opportunities for additional enhancement after developing the core-shell hetero-architecture with other metal oxide materials such as MnO2, and TiO2.

Mesoporous layered hexagonal platelets of Co3O4 nanoparticles with (111) facets for battery applications: high performance and ultra-high rate capability.

The thermally stable and crystalline 2D layered mesoporous hexagonal platelets of cobalt oxide (Co3O4) with (111) facets were prepared by using the template-free wet chemical synthesis approach. The high surface energy (111) facets known for a highly electroactive surface are expected to enhance the electrochemical properties, especially the rate capability. The highly crystalline Co3O4 with an average particle size of 25 nm formed a 2D mesoporous layered structure, with an average thickness of ∼40 nm, a pore size of 8-10 nm, and a specific surface area of 45.68 m2 g-1 promoting large surface confined electrochemical reaction. The 2D layered mesoporous Co3O4 exhibits a maximum specific capacity of 305 mA h g-1 at a scan rate of 5 mV s-1 and 137.6 mA h g-1 at a current density of 434.8 mA g-1. The maximum energy and power densities of 32.03 W h kg-1 and 9.36 kW kg-1, respectively, are achieved from the 2D hexagonal platelets of mesoporous Co3O4 nanoparticles with (111) facets. An excellent ultra-high rate capability of ∼62% capacity retention was observed after increasing the discharge current density from ∼434.8 mA g-1 to 43 480 mA g-1. Furthermore, a cycling stability of 81.25% was achieved even after 2020 charge-discharge cycles at a current density of 12 170 mA g-1. This high performance and ultra-high rate capability could be attributed to the (111) facets 'crystal plane' effect of Co3O4. Our results presented here confirm that the 2D mesoporous layered hexagonal platelets of Co3O4 exhibit "battery-mimic" behaviour in an aqueous electrolyte of KOH.

The effect of stoichiometry on the structural, thermal and electronic properties of thermally decomposed nickel oxide.

A thermal decomposition route with different sintering temperatures was employed to prepare non-stoichiometric nickel oxide (Ni1-δ O) from Ni(NO3)2·6H2O as a precursor. The non-stoichiometry of samples was then studied chemically by iodometric titration, wherein the concentration of Ni3+ determined by chemical analysis, which is increasing with increasing excess of oxygen or reducing the sintering temperature from the stoichiometric NiO; it decreases as sintering temperature increases. These results were corroborated by the excess oxygen obtained from the thermo-gravimetric analysis (TGA). X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) techniques indicate the crystalline nature, Ni-O bond vibrations and cubic structural phase of Ni1-δ O. The change in oxidation state of nickel from Ni3+ to Ni2+ were seen in the X-ray photoelectron spectroscopy (XPS) analysis and found to be completely saturated in Ni2+ as the sintering temperature reaches 700 °C. This analysis accounts for the implication of non-stoichiometric on the magnetization data, which indicate a shift in antiferromagnetic ordering temperature (T N) due to associated increased magnetic disorder. A sharp transition in the specific heat capacity at T N and a shift towards lower temperature are also evidenced with respect to the non-stoichiometry of the system.

Spitzer shaped ZnO nanostructures for enhancement of field electron emission behaviors.

We observed enhanced field emission (FE) behavior for spitzer shaped ZnO nanowires synthesized via a hydrothermal approach. The spitzer shaped and pointed tipped 1D ZnO nanowires of average diameter 120 nm and length ∼5-6 µm were randomly grown over an ITO coated glass substrate. The turn-on field (E on) of 1.56 V µm-1 required to draw a current density of 10 µA cm-2 from these spitzer shaped ZnO nanowires is significantly lower than that of pristine and doped ZnO nanostructures, and MoS2@TiO2 heterostructure based FE devices. The orthodoxy test that was performed confirms the feasibility of a field enhancement factor (ß FE) of 3924 for ZnO/ITO emitters. The enhancement in FE behavior can be attributed to the spitzer shaped nanotips, sharply pointed nanotips and individual dispersion of the ZnO nanowires. The ZnO/ITO emitters exhibited very stable electron emission with average current fluctuations of ±5%. Our investigations suggest that the spitzer shaped ZnO nanowires have potential for further improving in electron emission and other functionalities after forming tunable nano-hetero-architectures with metal or conducting materials.

Nano-Heteroarchitectures of Two-Dimensional MoS2@ One-Dimensional Brookite TiO2 Nanorods: Prominent Electron Emitters for Displays.

We report comparative field electron emission (FE) studies on a large-area array of two-dimensional MoS2-coated @ one-dimensional (1D) brookite (ß) TiO2 nanorods synthesized on Si substrate utilizing hot-filament metal vapor deposition technique and pulsed laser deposition method, independently. The 10 nm wide and 760 nm long 1D ß-TiO2 nanorods were coated with MoS2 layers of thickness ∼4 (±2), 20 (±3), and 40 (±3) nm. The turn-on field (E on) of 2.5 V/µm required to a draw current density of 10 µA/cm2 observed for MoS2-coated 1D ß-TiO2 nanorods emitters is significantly lower than that of doped/undoped 1D TiO2 nanostructures, pristine MoS2 sheets, MoS2@SnO2, and TiO2@MoS2 heterostructure-based field emitters. The orthodoxy test confirms the viability of the field emission measurements, specifically field enhancement factor (ßFE) of the MoS2@TiO2/Si emitters. The enhanced FE behavior of the MoS2@TiO2/Si emitter can be attributed to the modulation of the electronic properties due to heterostructure and interface effects, in addition to the high aspect ratio of the vertically aligned TiO2 nanorods. Furthermore, these MoS2@TiO2/Si emitters exhibit better emission stability. The results obtained herein suggest that the heteroarchitecture of MoS2@ß-TiO2 nanorods holds the potential for their applications in FE-based nanoelectronic devices such as displays and electron sources. Moreover, the strategy employed here to enhance the FE behavior via rational design of heteroarchitecture structure can be further extended to improve other functionalities of various nanomaterials.

Impact of Nanosize on Supercapacitance: Study of 1D Nanorods and 2D Thin-Films of Nickel Oxide.

We synthesized unique one-dimensional (1D) nanorods and two-dimensional (2D) thin-films of NiO on indium-tin-oxide thin-films using a hot-filament metal-oxide vapor deposition technique. The 1D nanorods have an average width and length of ∼100 and ∼500 nm, respectively, and the densely packed 2D thin-films have an average thickness of ∼500 nm. The 1D nanorods perform as parallel units for charge storing. However, the 2D thin-films act as one single unit for charge storing. The 2D thin-films possess a high specific capacitance of ∼746 F/g compared to 1D nanorods (∼230 F/g) using galvanostatic charge-discharge measurements at a current density of 3 A/g. Because the 1D NiO nanorods provide more plentiful surface areas than those of the 2D thin-films, they are fully active at the first few cycles. However, the capacitance retention of the 1D nanorods decays faster than that of the 2D thin-films. Also, the 1D NiO nanorods suffer from instability due to the fast electrochemical dissolution and high nanocontact resistance. Electrochemical impedance spectroscopy verifies that the low dimensionality of the 1D NiO nanorods induces the unavoidable effects that lead them to have poor supercapacitive performances. On the other hand, the slow electrochemical dissolution and small contact resistance in the 2D NiO thin-films favor to achieve high specific capacitance and great stability.

Photoluminescence mechanisms of metallic Zn nanospheres, semiconducting ZnO nanoballoons, and metal-semiconductor Zn/ZnO nanospheres.

We utilized a thermal radiation method to synthesize semiconducting hollow ZnO nanoballoons and metal-semiconductor concentric solid Zn/ZnO nanospheres from metallic solid Zn nanospheres. The chemical properties, crystalline structures, and photoluminescence mechanisms for the metallic solid Zn nanospheres, semiconducting hollow ZnO nanoballoons, and metal-semiconductor concentric solid Zn/ZnO nanospheres are presented. The PL emissions of the metallic Zn solid nanospheres are mainly dependent on the electron transitions between the Fermi level (E(F)) and the 3d band, while those of the semiconducting hollow ZnO nanoballoons are ascribed to the near band edge (NBE) and deep level electron transitions. The PL emissions of the metal-semiconductor concentric solid Zn/ZnO nanospheres are attributed to the electron transitions across the metal-semiconductor junction, from the E(F) to the valence and 3d bands, and from the interface states to the valence band. All three nanostructures are excellent room-temperature light emitters.

An efficient methodology for measurement of the average electrical properties of single one-dimensional NiO nanorods.

We utilized a metal tantalum (Ta) ball-probe to measure the electrical properties of vertical-aligned one-dimensional (1D) nickel-oxide (NiO) nanorods. The 1D NiO nanorods (on average, ~105 nm wide and ~700 nm long) are synthesized using the hot-filament metal-oxide vapor deposition (HFMOVD) technique, and they are cubic phased and have a wide bandgap of 3.68 eV. When the 1D NiO nanorods are arranged in a large-area array in ohmic-contact with the Ta ball-probe, they acted as many parallel resistors. By means of a rigorous calculation, we can easily acquire the average resistance RNR and resistivity ρNR of a single NiO nanorod, which were approximately 3.1 × 10(13) Ω and 4.9 × 10(7) Ω.cm, respectively.

Nanoscale dynamic behavior of surface magnetic domains on a La0.7Sr0.3MnO3 thin film.

An oscillating magnetic tip can be used to induce the striped magnetic ripple pattern with alternating up-and-down striped magnetic domains on a ferromagnetic La0.7Sr0.3MnO3 (LSMO) thin film surface. Magnetic force microscopy (MFM) images show that the surface magnetic domains (SMDs) can be aligned in a well-ordered alternating up-and-down c(2 x 2) structure on the stripe magnetic domains, indicating that the oscillating magnetic tip turns the ferromagnetic LSMO surface into a canted antiferromagnetic state. The orientation of the SMDs is determined by their discrete phase distribution. A three-dimensional (3D) SMD orientation model is built to understand dynamic behavior of the SMDs.

Effective photoluminescence in a large-area array of Ta2O5 nanodots.

We describe here the synthesis of a large-area Ta2O5 nanodot array by utilizing the hot filament metal vapor deposition technique. The Ta2O5 nanodots arranged in a large-area array on a Si wafer had an average diameter of -8 nm. X-ray photoemission spectroscopy (XPS) revealed the stoichiometric Ta and O compositions of the Ta2O5 nanodots. Raman spectroscopy showed the Ta2O5 nanodots to be of orthorhombic (beta) crystal. Photoluminescence (PL) spectroscopy showed the green and red light emissions of the beta-Ta2O5 nanodots at room temperature.

PbS quantum dot sensitized anatase TiO2 nanocorals for quantum dot-sensitized solar cell applications.

Lead sulphide (PbS) quantum dot (QD) sensitized anatase TiO(2) nanocorals (TNC) were synthesized by SILAR and hydrothermal techniques. The TNC, PbS and PbS-TNC samples were characterized by optical absorption, XRD, FT-IR, FESEM and XPS. The results show that PbS QDs are coated on the TNCs, the optical absorption is found to be enhanced and the band edge is shifted to ~693 nm as compared with plain TNCs at 340 nm. The PbS-TNC sample exhibits an improved photoelectrochemical performance with a maximum short circuit current (J(sc)) of 3.84 mA cm(-2). The photocurrent density was found to be enhanced 2 fold, as compared with those of the bare PbS photoelectrode. The total power conversion efficiency of the PbS-TNC electrodes is 1.23%.

Scanning photoemission spectromicroscopic study of 4-nm ultrathin SiO(3.4) protrusions probe-induced on the native SiO(2) layer.

Atomic force microscopy probe-induced large-area ultrathin SiO(x) (x ≡ O/Si content ratio and x > 2) protrusions only a few nanometers high on a SiO(2) layer were characterized by scanning photoemission microscopy (SPEM) and X-ray photoemission spectroscopy (XPS). SPEM images of the large-area ultrathin SiO(x) protrusions directly showed the surface chemical distribution and chemical state specifications. The peak intensity ratios of the XPS spectra of the large-area ultrathin SiO(x) protrusions provided the elemental quantification of the Si 2p core levels and Si oxidation states (such as the Si(4+), Si(3+), Si(2+), and Si(1+) species). The O/Si content ratio (x) was evidently determined by the height of the large-area ultrathin SiO(x) protrusions.

Two-dimensional single-crystalline Zn hexagonal nanoplates: size-controllable synthesis and X-ray diffraction study.

We synthesized two-dimensional (2D) Zn hexagonal nanoplates using the thermal metal-vapor deposition technique. An increase and decrease in the surface area and thickness of the 2D Zn hexagonal nanoplates were shown with elevated annealing temperatures, indicating their sizes to be controlled using the annealing treatment. X-Ray diffractometry (XRD) studies revealed the crystalline nature of the 2D Zn hexagonal nanoplates and the diffraction intensity of the (002) lattice plane, which increased parabolically with elevated annealing temperatures.

Enhancement of green-light photoluminescence of Ta2O5 nanoblock stacks.

In this study we have explored the structural, electronic, and photoluminescence (PL) properties of Ta(2)O(5) nanoblock stacks. The Ta(2)O(5) nanoblocks were synthesized by the hot filament metal-oxide vapor deposition (HFMOVD) technique and randomly arranged in large-area stacks. Field-emission scanning electron microscopy (FESEM) showed most of the stacking Ta(2)O(5) nanoblocks to be 21 nm wide. Energy dispersive spectroscopy (EDS) analysis verified the presence of only the elements Ta and O. X-Ray photoemission spectroscopy (XPS) not only revealed the electronic structures and chemical properties of the stacking Ta(2)O(5) nanoblocks but also their stoichiometric Ta/O ratio of ∼0.416 (i.e. Ta:O = 2.08 : 5). Photoluminescence (PL) spectroscopy showed very strong green-light emissions, which emerged from the trap-levels of the oxygen vacancies within the Ta(2)O(5) bandgap. The PL intensities were linearly enhanced by increasing the laser power and the excitation time. The PL results suggest that the nanoblocks are excellent visible-light emitters.

Creation and manipulation of surface magnetic domains in an alternating up-and-down pattern.

According to Lenz's law, the magnetic field from the oscillating magnetic probe will induce out-of-plane surface magnetic domains (SMDs) from the in-plane magnetization at the locally tapped points on a ferromagnetic La(0.7)Sr(0.3)MnO3 (LSMO) thin film. It was possible to control and manipulate the out-of-plane SMDs by varying the tapping intervals and changing the scanning direction. We also found that the anisotropic stresses from the out-of-plane SMDs caused the appearance of large-area straight striped domain structures on the order of several micrometers. Smaller oscillating magnetic probe tapping intervals produced larger periods (or widths) of the straight striped domain structure.

High room-temperature photoluminescence of one-dimensional Ta2O5 nanorod arrays.

In this study we analyzed the structural and electronic properties of a new morphological form, one-dimensional (1D) Ta2O5 nanorod arrays, which were synthesized by hot filament metal vapor deposition. Field-emission scanning electron microscopy (FESEM) showed the 1D Ta2O5 nanorods to be arranged in a large-area high-density array about 50 nm wide and approximately 550 nm long. X-ray photoemission spectroscopy (XPS) revealed not only the electronic structures and chemical properties of the 1D Ta2O5 nanorods but also their stoichiometric Ta and O compositions. Photoluminescence (PL) spectra showed intensive green-light, yellow-light and red-light emissions at room temperature. These emissions simultaneously emerged from the trap levels of oxygen vacancies within the Ta2O5 bandgap. The emission results strongly indicate that the 1D Ta2O5 nanorods are good room-temperature visible-light emitters.