One-step hydrothermal synthesis of hybrid core-shell Co3O4@SnO2–SnO for supercapacitor electrodes

We successfully synthesized a novel core-shell hybrid metal oxide via a simple one-step hydrothermal method without annealing. This composite of Co₃O₄ particles covered with SnO₂–SnO (Co₃O₄@SnO₂–SnO) predicted better performance compared to pure Co₃O₄, which strongly depends on the synthetic temperature. The Co₃O₄@SnO₂–SnO prepared at a temperature of 250 °C (labeled Co₃O₄@SnO₂–SnO-250) exhibited an outstanding specific capacitance of 325 F g⁻¹ under the current density of 1 A g⁻¹, which was much higher than those of Co₃O₄ (12.6 F g⁻¹) and other composites. Additionally, the sample also exhibited good cycle stability performance with a retention rate of 100% after 5000 cycles at a current density of 5 A g⁻¹. Through X-ray photoelectron spectroscopy analysis, the presumed mechanism was that Sn-O_x decreases the surface electron densities of Co₃O₄, which is beneficial to OH⁻ adsorption and specific capacitance improvement, and the synthetic temperature had a strong impact on the microstructure and thus on the surface electron densities. The most.obvious finding to emerge from this study is that the specific capacitance can be improved through adjusting the surface electron densities of transition metal oxides.     

Cavity-like hierarchical architecture of WS2/α-NiMoO4 electrodes for supercapacitor application

In this study, we fabricated a nano/micro cavity-like hierarchical architecture of WS₂/α-NiMoO₄ composite using microwave hydrothermal and calcination processes. The composite was characterized by X-ray diffraction, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, elemental mapping, and X-ray photoelectron spectroscopy. The electrochemical measurements of the WS₂/α-NiMoO₄ composite electrode for application in supercapacitors (SCs) were performed through cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. The WS₂/α-NiMoO₄ nanocomposite exhibited a specific capacity of 460 F g^-1 at 1 A g^-1 current density and a capacitor retention of 92% after 2000 cycles. However, α-NiMoO₄ spherical nanoparticles had a specific capacity of 231 F g^-1 at 1 A g^-1 current density and capacitor retention of 73% after 2000 cycles. The excellent specific area, formation of cavity-like structures, increase in pore size, superior electrical conductivity, and robust stability of WS₂/α-NiMoO₄ enhanced the effectiveness of the electrode composite material for supercapacitor application.     

Sol-gel synthesis of MnxGa1−xFe2O4 nanoparticles as candidates for hyperthermia treatment

Sol-gel synthesis of novel Mn_xGa_1−xFe₂O₄ (x=0–1) magnetic nanoparticles (MNP's) was studied. An inverse spinel crystalline structure was identified for all samples. Magnetization saturation values (Ms) were in the range of 21.4–42.6 emu/g, while coercive field (Hc) was less than 27.4 Oe in all cases. Selected compositions of Mn_xGa_1−xFe₂O₄ (x=0.6, 0.8) showed nanoparticles with near-spherical morphology and average size of 15 nm. Magnetic induction curves indicate that a suspension concentration of MNP's equal or higher than 4.5 mg/mL was sufficient to reach the temperature required for hyperthermia treatment (>43 °C) in less than 10 min. The incorporation of Mn ions into the crystalline structure led to an increase of the magnetic response of the MNP's when an alternate magnetic field was applied, requiring a shorter time of exposition and a low dose of MNP's, which make these nanoparticles potential candidates for magnetic hyperthermia.     

Effect of mechanochemical synthesis on the structure,magnetic and optical behavior of Ni1−xZnxFe2O4 spinel ferrites

Ni_1−xZn_xFe₂O₄ (0≤x≤1) nanocrystals were prepared by a soft mechanochemical approach. The structure and morphology were assessed via X-ray powder diffractometery (XRD), infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM) and Energy dispersive spectroscopy (EDS). The magnetic characteristics have been evaluated using vibrating sample magnetometer (VSM). The optical properties were explored by diffuse reflectance UV–visible spectrophotometry (DRS). The substitution of Zn into the Ni_1−xZn_xFe₂O₄ nanocrystals increased the mean nanocrystal size from 4 to 19 nm. The FTIR and Raman spectroscopies showed that the substitution with Zn up to x=0.5 in Ni_1−xZn_xFe₂O₄ nanocrystals results in a migration of Fe ions from tetrahedral to octahedral sites, leading to an improvement of the saturation magnetization value to 33.8 emu/g. At the same time, the optical band gap decreased from 2.6 to 1.93 eV due to the increase of the Zn content from x=0 to x=1. These promising characteristics of Ni_1−xZn_xFe₂O₄ nanocrystals make them suitable for the use in the field of magnetically recoverable catalysts including those for energy applications.     

Sol–gel mediated surface modification of nanocrystalline NiFe2O4 spinel powders with amorphous SiO2

Surface modification of nanocrystalline NiFe₂O₄ spinel particles with amorphous SiO₂ by the sol–gel process at 350 °C was demonstrated. Amorphous phase of the SiO₂ layer was evaluated by X-ray diffraction technique. Structural coordination of the pristine and SiO₂ coated NiFe₂O₄ particles as investigated by employing FTIR analysis. Thickness of the SiO₂ layer was investigated through transmission electron microscopy and it was identified to be ～10–23 nm over nanocrystalline NiFe₂O₄ particles. The magnetic behavior of pristine and surface modified NiFe₂O₄ particles were investigated using vibrating sample magnetometer (VSM). Magnetic studies showed the retention of magnetic property of surface modified NiFe₂O₄ particles with the reduced saturation magnetization and coercivity compared to the pristine NiFe₂O₄ particles, which is respectively due to the lower fraction of the magnetic component and the formation of interfacial structure.     

Structural and electrical properties of magnetic ceramics of Co1−xCuxFe2O4 spinel nanoferrites

Abstract

Magnetic ceramics of the type of spinel nanoferrites of Co_1?xCu_xFe₂O₄ with Cu concentrations of x?=?0·00, 0·25, 0·50, 0·75 and 1·00 were prepared by chemical co-precipitation method. X-ray diffraction results confirmed the formation of a single spinel ferrite structure with crystallite size in the range of 20–63 nm. Scanning electron microscopy and EDS were used to study the morphological and compositional changes taking place with varying Cu concentration. DC electrical resistivity, activation energy and drift mobility are strongly influenced by both Cu concentration and temperature. Resistivities of the prepared magnetic ceramics were found to decrease with the increase in Cu concentration to follow Verwey mechanism. The semiconductor behaviour of the prepared nanoparticles was confirmed from the standard Arrhenius relation of resistivity versus temperature. The dielectric constants were measured in the frequency range of 100 Hz–3·0 MHz and are explained by the Maxwell–Wagner interfacial type of polarisation.     

Hydrothermal synthesis and characterization of nanorods “LixV2−δO4−δ·H2O”

Nanorods “Li_xV_2−δO_4−δ·H₂O” were hydrothermally synthesized with starting agents LiOH·H₂O and V₂O₅, and reducing agent hydrazine monohydrate (NH₂NH₂·H₂O) under alkaline condition at 160 °C. The samples were characterizated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The nanorods obtained have diameters from 80 to 100 nm with length up to several micrometers. Molecular coordination and assembly mechanism can be assumed to explain the formation of one-dimensional nanorods.     

Improvement of the magnetoelectric response in NiFe2O4−Sr0.5Ba0.5Nb2O6 composites using LiNbO3 as sintering additive

Magnetoelectric (NiFe₂O₄)_0.3−(Sr_0.5Ba_0.5Nb₂O₆)_0.7 composites with addition of LiNbO₃ as sintering additive were prepared by a classical mixed-oxide method. XRD patterns of ceramics sintered between 1000 and 1200 °C show the desired Sr_0.5Ba_0.5Nb₂O₆ and NiFe₂O₄ phases. SEM investigations confirm the 0–3 connectivity of the composite ceramics. The addition of 10 and 20 mol% LiNbO₃ improves the densification of the composite ceramics and leads to an increase of the size of the Sr_0.5Ba_0.5Nb₂O₆ grains. Magnetic measurements show hystereses with low coercivities. Dielectric measurements were carried out depending on temperature and frequency. The samples with the LiNbO₃ addition show significantly higher resistivity values (σ_DC). Magnetoelectric measurements were carried out in dependence of the magnetic DC-field, temperature, and frequency. The maximum magnetoelectric coefficient (α_ME) rises with the addition of LiNbO₃ from 180 to 803 µV Oe⁻¹ cm⁻¹ (@900 Hz). Temperature dependent measurements show a continuously decreasing of α_ME with lower temperature.     

Microstructure of single-phase cobalt and manganese oxide spinel Mn3−xCoxO4 ceramics

This paper reports microstructural studies of single-phase Mn_3−xCo_xO₄ (0.98 ≤ x ≤ 2.93) spinel ceramics using transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). These ceramics were obtained by conventional sintering or by spark plasma sintering (SPS) of powders prepared by thermal decomposition of coprecipitated oxalate precursors. For x < 1.78 or x ≥ 1.78, the monophasic ceramics correspond respectively to quadratic (Q) or cubic (C) spinel structure. The ferroelastic character of the structural phase transition from C to Q is highlighted by specific microstructural features. The effect of chemical composition and heat treatment conditions on the microstructure and essentially on the presence and the characteristics of twins were investigated. The coherent twin interfaces are parallel to (1 1 2) planes in the Q cell. Twins can correspond to: tweeds, single lamellae (widths: 5–306 nm) arranged parallel to each other, large lamellae (widths: 69–928 nm) internally twinned and sometimes arranged in cyclic forms (triangular shapes).     

Hydrothermal solvothermal synthesis and microwave absorbing study of MCo2O4 (M = Mn,Ni) microparticles

ABSTRACT

MCo₂O₄ (M?=?Mn,Ni) microparticles were synthesised by a simple hydrothermal solvothermal method. The samples were characterised by X-ray diffraction, X-ray energy dispersive spectroscopy and scanning electron microscopy, which showed that MnCo₂O₄ microparticles with spherical particles aggregated by a large number of small cubes and cubic shaped NiCo₂O₄ microcubes were obtained. The microwave absorption properties of these products were systematically investigated by vector network analysis. Results indicated that the minimum reflection loss value of MnCo₂O₄ microparticles was ?26.34?dB at 11.04?GHz with the absorber thickness of 2.5?mm, which was much lower than that of NiCo₂O₄ microcubes with the same absorber thickness. The possible mechanism was analysed, indicating that the geometry and size of MCo₂O₄ (M?=?Mn,Ni) microparticles played a key role in microwave absorption.     

Ni0.4Co x Cd0.6 − x Fe2O4 ferrites as prepared by autocombustion synthesis

Ni_0.4Co _x Cd_0.6?x Fe₂O₄ ferrites (x = 0.0, 0.2, 0.4, and 0.6) were prepared by autocombustion synthesis and characterized by XRD, SEM, and other physical methods. XRD reveals the formation of spinel structure without any impurity phase. With increasing x, the lattice parameter was found to decrease from 8.60 to 8.37 Å. The FTIR spectra show the presence of tetrahedral site (at 571.12 cm^?1) and octahedral site (at 407.07 cm^?1). SEM images indicated the formation of agglomerated grains with a size of about 4.3 μm. The resistivity of the ferrites was found to decrease from 24.53 to 10.02 × 10⁸ Ω cm while the drift mobility to increase from 2.30 to 4.41 × 10⁸ cm² V^?1 s^?1 with increasing x.     

Straightforward synthesis of hierarchical Co3O4@CoWO4/rGO core–shell arrays on Ni as hybrid electrodes for asymmetric supercapacitors

Hierarchical Co₃O₄@CoWO₄/rGO core/shell nanoneedles arrays are successfully grown on 3D nickel foam using a simple, effective method. By virtue of its unique structure, Co₃O₄@CoWO₄/rGO demonstrates an enhanced specific capacitance of 386 F g⁻¹ at 0.5 A g⁻¹ current density. It can be used as an integrated, additive-free electrode for supercapacitors that boasts excellent performance. As illustration, we assemble an asymmetric supercapacitor (ASC) using the as-prepared Co₃O₄@CoWO₄/rGO as the positive electrode and activated carbon as the negative electrode. The optimized ASC displays a maximum energy density of 19.99 Wh kg⁻¹ at a power density of 321 W kg⁻¹. Furthermore, the ASC also presents a remarkably long cycle life along with 88.8% specific capacitance retention after 5000 cycles.     

One-step synthesis of nitriles by the dehydrogenation–amination of fatty primary alcohols over Cu/m-ZrO2

An effective method for one-step synthesis of nitriles employing C₂–C₈ fatty primary alcohols and ammonia over 5%Cu/m-ZrO₂ has been found. The conversion of alcohols and selectivity of nitriles obtained are > 96 and > 87 wt.%, respectively, and are obviously influenced by the C2-substitution rather than the chain length of fatty primary alcohols. Cu/m-ZrO₂ was characterized by XRD, H₂-TPR, CO₂-TPD and NH₃-TPD. It is revealed that a substantial amount of Cu species over m-ZrO₂ is in highly dispersed CuO. A plausible mechanism is proposed and supported by different experiments, and aldehyde generation is an important step in the reaction mechanism.     

Extremely high corrosion resistance of ZnxNi1–xCr2O4 spinel as sidewalls in the aluminum electrolyte

The sidewall material is a key component in new electrolytic cell with an inert electrode for the aluminum electrolysis industry. The continuous development of novel sidewall materials with excellent corrosion resistance in molten salts electrolyte is an important topic. Herein, a new system of sidewall material, spinel structured Zn_xNi_1–xCr₂O₄ (x = 0 – 1), is prepared by solid-phase reaction and the corrosion-resistance enhancement is investigated. The results prove that Zn²⁺ plays two roles in the Zn_xNi_1–xCr₂O₄ spinels. Firstly, Zn²⁺ tunes the surface energies of spinels resulting in the octahedral grains, which suppresses the cation diffusion in the corrosion process. Secondly, Zn²⁺ stabilizes the Cr³⁺ in the spinels. As a result, the Zn_0.5Ni_0.5Cr₂O₄ spinel displays an extremely low corrosion rate ～0.007 cm·a^–1 in NaF-KF-AlF₃ bath at 800 °C comparing with other sidewall materials. The as-obtained spinel shows great potential as a novel sidewall material for the new electrolytic cell.     

Preparation of spherical α-Al2O3 nanoparticles by microwave hydrothermal synthesis and addition of nano-Al seeds

Due to their special appearance, spherical α-Al₂O₃ nanoparticles play an important role for obtaining high-performance structural and functional ceramics. However, there are still problems such as easily agglomerates to form worm-like structures at high temperatures and difficult availability of spherical nanoparticles. In this study, spherical α-Al₂O₃ nanoparticles with high dispersion were prepared by a combination of a microwave hydrothermal method and an addition of nano-Al particles as seeds. First, spherical amorphous alumina precursors were synthesized by the microwave hydrothermal method at 100°C for 30 min using Al₂(SO₄)₃·18H₂O, Al(NO₃)₃·9H₂O, and urea, as raw materials, and then spherical α-Al₂O₃ nanoparticles with a diameter of about 66 nm were acquired after calcined the precursor at 1050°C for 90 min by adding nano-Al seeds, which reduced the calcination temperature by 50°C and holding time by 30 min compared to that without seeds. Kinetic analysis shows that 5 wt.% nano-Al seeds can reduce the activation energy of crystalline transition of γ-Al₂O₃ to α-Al₂O₃ from 516.51 to 474.37 kJ/mol. Moreover, the microscopic mechanism of nano-Al particles as seeds was investigated. The characterizations of sintering properties show that spherical α-Al₂O₃ nanoparticles facilitate the acquisition of uniform microstructure for resulting ceramic and the fracture modes include both intergranular and transgranular fractures.     

Cu-substituted La2NiO4+δ as oxygen electrodes for protonic ceramic electrochemical cells

In order to overcome different tasks related to the thermal and chemical compatibility of functional solid oxide electrochemical cell materials, including those based on proton-conducting electrolytes, the search for new potential oxygen/steam electrodes is of great interest. In the present work, the Lа₂Ni_1–хCu_xO_4+δ (LNCx, x = 0. 0.1, 0.2 and 0.3) compounds, which constitute a class of Co-free and alkaline-earth elements (AEE)-free layered materials, were successfully synthesised and then studied as possible oxygen electrodes for protonic ceramic fuel cells. A complex of methods was used to comprehensively analyse the individual characteristics of LNCx (structural parameters, oxygen overstoichiometry, thermal expansion, total conductivity) as well as their properties in symmetrical and fuel cell architectures (polarisation resistance, performance). According to the obtained results, a slight degree of Ni with Cu substitution can be used for optimising the functional properties of LNCx, such as low sintering temperatures of cathode formation, low thermal expansion coefficients, good electronic conductivity and sufficient electrochemical activity (including under conditions of moisturised atmospheres). Therefore, the LNCx cathodes can be considered as one of the possible Co- and AEE-free candidates for intermediate-temperature protonic ceramic electrochemical cells.     

One-step chemical vapor deposition synthesis of magnetic CNT–hercynite (FeAl2O4) hybrids with good aqueous colloidal stability

A multiwall carbon nanotube (MWCNT)/hercynite (FeAl₂O₄) hybrid nanomaterial was synthesized by one-step chemical vapor deposition (CVD) using acetylene as precursor and FeO_x–AlOOH xerogel as catalyst. The hybrid material was composing by hercynite nanoparticles (diameter 10–50 nm) intimately attached to the walls of the MWCNTs. The diameter of the MWCNTs was related to particle size of the catalyst. The hybrid nanomaterial exhibited a characteristic magnetic behavior that can be considered as a combination of superparamagnetism and ferromagnetism, with a saturation magnetization of 5.7 emu/g at an applied field of 18 kOe and a coercivity of 520 Oe. The hybrid displayed a relatively low pH_ZPC (approx. 3.2) and formed very stable aqueous suspensions at pH 5.5. Controlled oxidation of the hybrid generated oxidized functional groups, as –OH and –COOH, and promoted the transformation of hercynite to hematite. Due to the high dispersibility of the hybrid in water, it presents an interesting potential as nanofiller for hydrophilic polymers.     

Improved magnetic and electromagnetic absorption properties of xSrFe12O19/(1−x)NiFe2O4 composites

xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites (0 ≤ x ≤ 1.0) were synthesized by using a conventional solid-state synthetic route. The results show that magnetic hysteresis loops of the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites are similar to those of individual component ferrites, except for the 0.1SrFe₁₂O₁₉/0.9NiFe₂O₄ and 0.3SrFe₁₂O₁₉/0.7NiFe₂O₄, suggesting that the hard/soft magnetic phases are well exchange-coupled. The saturation magnetization, coercivity, and remanent magnetization of the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites are increased with increasing content of SrFe₁₂O₁₉, with maximal values of 42.1 Am² kg⁻¹, 78.7 kA m⁻¹, 17.2 Am² kg⁻¹, respectively, as the content x is about 0.5. They are higher than those of the individual components, implying that interface coupling is present in the magnetic composites. The coercivity and remanent magnetization of the composites are increased initially with increasing sintering temperature and then show a downward tendency. For the component SrFe₁₂O₁₉ and NiFe₂O₄, the minimum reflection losses are −12.5 dB and −18.3 dB at match thicknesses of 2.5 mm and 2 mm, respectively. Compared with those of the component SrFe₁₂O₁₉ and NiFe₂O₄, the microwave absorption performances of the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites are improved remarkably, especially for the samples of x = 0.3 and x = 0.9. The minimum reflection losses values of the 0.3SrFe₁₂O₁₉/0.7NiFe₂O₄ composite are −31.6 dB (12.7 GHz) and −20.2 dB (13 GHz), while those of the 0.9SrFe₁₂O₁₉/0.1NiFe₂O₄ composites are −23.7 dB (16.3 GHz) and −33.5 dB (15.8 GHz), as the matching thicknesses are 2.5 mm and 2 mm, respectively. Therefore, the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites could be used as potential microwave absorption materials.     

Preparation and electrochemical characterization of Ti/Ru x Mn1−x O2 electrodes

DSA^® type electrodes of ruthenium–manganese mixed oxides (30 at % Ru < 100) supported on titanium were prepared by the spray-pyrolysis technique, using Ru(NO)(OH) _x (NO₃)_3–x and Mn(NO₃)₂ as precursors. Electrodes were characterized by SEM, XRD and cyclic voltammetry. Their behaviour as anode for the chlorine and oxygen evolution reactions was also evaluated by polarization curves. The stability of the mixed oxides was determined through accelerated tests of service life. It has been verified that the best performance on the apparent electrocatalytic activity of both reactions as well as on stability is achieved at a composition of about 70% Ru.