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Ti3C2-X MXenes have attracted tremendous research interest because their 2D laminar morphology provides numerous functional applications. The application options rely on the purity and interlayer spacing of MXenes, which eventually depend on the purity of the MAX phase. This motivated us to synthesize pure MAX phases to produce MXenes at large scale using simpler and less expensive techniques. However, producing prerequisite pure MAX phases at atmospheric pressure and relatively lower temperatures is still a challenging task. This study reports the synthesis of thermally stable pure MAX phases (and MXenes) by systematically varying the molar ratio of the precursors, reaction temperature, and reaction time using a novel MS5 process under atmospheric pressure conditions. The purity of MAX phases under different synthesis conditions shows a direct interrelationship with the 2D laminar morphology of MXenes. The highest purity of >99% for the MAX phase was achieved by reacting Ti : Al : C precursors in a 3 : 1.5 : 1.9 molar ratio at 1350 °C for 90 min and delivered highly distinctive 2D nanostructured laminar MXenes with larger interlayer spacing and specific surface area (i.e., 8.8 ± 0.1 m2 g-1), which are superior to those in previously reported works. These results reveal that the precursor molar ratios and reaction conditions tailor the MAX phase purity, thereupon, they are crucial for achieving good quality 2D laminar MXenes with large specific surface areas, further enhancing the performance of MXene-related devices. The developed MS5-MXenes, when probed as electrodes for Na ion applications, show excellent initial and reversible capacity values of 142 mA h g-1 and 103 mA h g-1 (at 50 mA g-1), respectively.
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Multifunctional photodetectors (PDs) with broadband responsivity (R) and specific detectivity (D*) at low light intensities are gaining significant attention. Thus, we report a bilayer PD creatively fabricated by layering two-dimensional (2D) Sb2Se3 nanoflakes (NFs) on one-dimensional (1D) ZnO nanorods (NRs) using simple thermal transfer and hydrothermal processes. The unique coupling of these two layers of materials in a nanostructured form, such as 2D-Sb2Se3 NFs/1D-ZnO NRs, provides an effective large surface area, robust charge transport paths, and light-trapping effects that enhance light harvesting. Furthermore, the combination of both layers can effectively facilitate photoactivity owing to proper band alignment. The as-fabricated device demonstrated superior overall performance in terms of a suitable bandwidth, good R, and high D* under low-intensity light, unlike the single-layered 1D-ZnO NRs and 2D-Sb2Se3 NF structures alone, which had poor detectivity or response in the measured spectral range. The PD demonstrated a spectral photoresponse ranging from ultraviolet (UV) to visible (220-628 nm) light at intensities as low as 0.15 mW·cm-2. The PD yielded a D* value of 3.15 × 1013 Jones (220 nm), which reached up to 5.95 × 1013 Jones in the visible light region (628 nm) at a 3 V bias. This study demonstrated that the 2D-Sb2Se3 NFs/1D-ZnO NRs PD has excellent potential for low-intensity light detection with a broad bandwidth, which is useful for signal communications and optoelectronic systems.
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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.
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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.
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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 â¢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.
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Corantes , Óxidos , Humanos , Cinética , Água , Vermelho Congo , Cátions , Violeta GencianaRESUMO
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.
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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 â¼0.416 (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.
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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.
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Técnicas Eletroquímicas/métodos , Microscopia de Força Atômica/métodos , Nanotecnologia , Semicondutores , Dióxido de Silício/química , Teste de Materiais , Microscopia de Força Atômica/instrumentação , Oxirredução , Espectroscopia Fotoeletrônica , Propriedades de Superfície , TemperaturaRESUMO
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.
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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.
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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 â¼670 nm, and were composed of nanoparticles of average diameter â¼41 nm. The well crystalline CTO microrods of the hexagonal phase to the R3Ì 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.
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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.
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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.
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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 â¼40 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 â¼62% capacity retention was observed after increasing the discharge current density from â¼434.8 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.
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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.
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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 â¼5-6 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.
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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 â¼4 (±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.
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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 â¼100 and â¼500 nm, respectively, and the densely packed 2D thin-films have an average thickness of â¼500 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 â¼746 F/g compared to 1D nanorods (â¼230 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.
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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.
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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.