Electrochemical supercapacitor studies of hierarchical structured Co2+-substituted SnO2 nanoparticles by a hydrothermal method

Hierarchical structured Co-doped SnO₂ nanoparticles are prepared by a low temperature hydrothermal process. The structural and surface morphologies of the SnO₂ and Sn_1?xCo_xO₂ nanoparticles are studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The Sn_1?xCo_xO₂ nanoparticles form with a tetragonal rutile structure during the hydrothermal process without further calcination. The pseudocapacitance behavior of the Sn_1?xCo_xO₂ nanoparticles is characterized by cyclic voltammetry (CV) in 1.0 M H₂SO₄ electrolyte. The specific capacitance (SC) is found to increase with an increase in cobalt content. A maximum SC of 840 F g^?1 is obtained for a Sn_0.96Co_0.04O₂ composite at a 10 mV s^?1 scan rate.     

Cobalt terephthalate MOF-templated synthesis of porous nano-crystalline Co3O4 by the new indirect solid state thermolysis as cathode material of asymmetric supercapacitor

In this work, two different types of Co₃O₄ nano-crystals were synthesized by (i) conventional direct solid state thermolysis of cobalt terephthalate metal-organic framework (MOF-71) and (ii) new indirect solid state thermolysis of Co(OH)₂ derived by alkaline aqueous treatment of MOF-71. The products were then characterized by X-ray diffraction technique (XRD), Fourier transforms infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Reflection electron energy loss spectroscopy (REELS), Brunauer, Emmett, and Teller (BET), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) techniques. By REELS analysis the energy band gap of MOF-71 was determined to be 3.7 eV. Further, electrochemical performance of each Co₃O₄ nanostructure was studied by the cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) in a three-electrode system in KOH electrolyte. An asymmetric supercapacitor was fabricated using indirect Co₃O₄ nanoparticles as cathode and electrochemically reduced graphene oxide as anode, and the electrochemical properties were studied and showed a high energy density of 13.51 Wh kg⁻¹ along with a power density of 9775 W kg⁻¹ and good cycling stability with capacitance retention rate of 85% after 2000 cycles.     

Preparation and electrochemical properties of mesoporous Co3O4 crater-like microspheres as supercapacitor electrode materials

Mesoporous Co₃O₄ microspheres with unique crater-like morphology were obtained by utilizing the mesoporous silica material MCM-41 as a template. The analysis results of N₂ adsorption–desorption measurement indicate that the product has a large Brunauer–Emmett–Teller (BET) surface area of 60 m² g⁻¹ and a narrow pore size distribution centering around 3.7 nm. Its electrochemical properties were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The findings reveal that this novel morphology material has a smaller inner resistance of about 0.4 Ω and a higher onset frequency of 550 Hz. This material can provide a high specific capacitance of 102 F g⁻¹ and a large capacity retention of 74% in 500 continuous cycles test at a sweep rate of 3 mV s⁻¹. More significantly, the mass loading of electroactive species can reach as large as 2 mg cm⁻², which is one order of magnitude larger than common amount used.     

Sonochemical synthesis of cobalt aluminate nanoparticles under various preparation parameters

Cobalt aluminate (CoAl₂O₄) nanoparticles were synthesized using a precursor method with the aid of ultrasound irradiation under various preparation parameters. The effects of the preparation parameters, such as the sonochemical reaction time and temperature, precipitation agents, calcination temperature and time on the formation of CoAl₂O₄ were investigated. The precursor on heating yields nanosized CoAl₂O₄ particles and both these nanoparticles and the precursor were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The use of ultrasound irradiation during the homogeneous precipitation of the precursor reduces the duration of the precipitation reaction. The mechanism of the formation of cobalt aluminate was investigated by means of Fourier transformation infrared spectroscopy (FT-IR) and EDX (energy dispersive X-ray). The thermal decomposition process and kinetics of the precursor of nanosized CoAl₂O₄ were investigated by means of differential scanning calorimetry (DSC) and thermogravimetry (TG). The apparent activation energy (E) and the pre-exponential constant (A) were 304.26 kJ/mol and 6.441 × 10¹⁴ s^?1, respectively. Specific surface area was investigated by means of Brunauer Emmett Teller (BET) surface area measurements.     

Sonochemical synthesis and characterization of Co3O4 nanocrystals in the presence of the ionic liquid [EMIM][BF4]

For the first time, a sonochemical process has been used to synthesis cobalt oxide Co₃O₄ nanoflowers and nanorods morphology in the presence of the ionic liquid 1-Ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF₄] as reaction media and morphology template. Different sonication time periods and different molar ratios of the ionic liquid (IL) were used to investigate their effects on the structural, optical, chemical and magnetic properties of the produced Co₃O₄ nanoparticles. During synthesis process brown powder contains cobalt hydroxide Co(OH)₂ and cobalt oxyhydroxide (Cobalt hydroxide oxide) CoO(OH) was formed, after calcination in air for 4 h at 400 °C a black powder of Co₃O₄ nanoparticles was produced. The produced Co₃O₄ nanoparticles properties were characterized by X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), transmission electron microscopy (TEM), FTIR spectroscopy, UV–vis spectroscopy, and Vibrating Sample Magnetometer (VSM). To explain the formation mechanism of Co₃O₄ NPs some investigations were carried on the brown powder before calcination.     

Structural and electronic properties of cobalt carbide Co2C and its surface stability: Density functional theory study

Density functional theory calculations have been performed to investigate the structural and electronic properties of bulk Co₂C and the stability of low index Co₂C surfaces. We found that the formation of Co₂C is exothermic with the formation energy of ? 0.81 eV/Co₂C with respect to Co under the presence of syngas (mixture of CO and H₂). While formed Co₂C can be decomposed further to metal Co and graphite carbon with modest energy gain of 0.37 eV/Co₂C. This suggests that Co₂C is only metastable in Fischer–Tropsch synthesis, which agrees well with experimental findings. The density of states (DOSs) reveals that the Co₂C is paramagnetic and strong metallic-like. The difference of charge density analysis indicates that the bond of Co₂C is of the mixtures of metallic, covalent, and ionic properties. A variety of low index Co₂C surfaces with different terminations are studied. We find that the surface energy of low index stoichiometric Co₂C highly relies on the surface area, the number of coordination of surface atoms and the surface dipole, with the decreased stability order of (101) > (011) > (010) > (110) > (100) > (001) = (111). Our results indicate that under Co-poor condition, the formation of non ? stoichiometric surface (011) and (111) without terminated cobalt is energetically more favorable, while under Co-rich condition the formation of non ? stoichiometric (111) surface with cobalt overlayer are preferential.     

Hydrothermal synthesis of single crystal MoO3 nanobelts and their electrochemical properties as cathode electrode materials for rechargeable lithium batteries

Orthorhombic phase MoO₃ (α-MoO₃) nanobelts with uniform diameter are successfully prepared through a hydrothermal synthesis route at a low temperature (180 °C) in the presence of cetyltrimethylammonium bromide (CTAB) using saturated solution of ammonium molybdate tetrahydrate (AHM) as well as nitrate as raw materials, and are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The CTAB plays a key role in the formation of α-MoO₃ nanobelts and the aspect ratio of nanobelts significantly varies with quality of CTAB. The nanobelts with rectangular cross-sections have single crystalline orthorhombic phase structure, preferentially grow in [001] direction. Raman shifts of the α-MoO₃ nanobelts are fully consistent with that of flaky structure; however, intensity ratio of peaks 818.3 cm^?1 and 991.2 cm^?1 of α-MoO₃ nanobelts remarkably changes comparing with that of lamellar MoO₃. Electrochemical properties of α-MoO₃ single crystal nanobelts synthesized as cathode electrode materials for rechargeable lithium batteries are also measured. It indicates that the α-MoO₃ nanobelts exhibit a better performance than MoO₃ micro flakes.     

Suppression of structural degradation of LiNi0.9Co0.1O2 cathode at 90 °C by AlPO4-nanoparticle coating

This study examined the electrochemical and structural stability of ∼1.5 wt.% AlPO₄-coated LiNi_0.9Co_0.1O₂. The AlPO₄-coated LiNi_0.9Co_0.1O₂ retained ∼60% of the original capacity after 50 cycles, compared with the ∼30% capacity retention of the bare LiNi_0.9Co_0.1O₂. The discharge profiles and cyclic voltammograms from 4.5 V at 90 °C for 4 h showed enhanced structural stability. Scanning electron microscopy and X-ray diffraction revealed that the AlPO₄-coated LiNi_0.9Co_0.1O₂ had less degradation than the bare LiNi_0.9Co_0.1O₂.     

Ultrasonic-assisted ultra-rapid synthesis of monodisperse meso-SiO2@Fe3O4 microspheres with enhanced mesoporous structure

A core–shell-type of meso-SiO₂@Fe₃O₄ microsphere was synthesized via an ultrasonic-assisted surfactant-templating process using solvothermal synthesized Fe₃O₄ as core, tetraethoxysilane (TEOS) as silica source, and cetyltrimethyl ammonium bromide (CTAB) as templates. The samples were characterized by FT-IR, XRD, TEM, N₂ adsorption–desorption technology, and vibrating sample magnetometer (VSM). The results show that as-prepared meso-SiO₂@Fe₃O₄(E) and meso-SiO₂@Fe₃O₄(C) microspheres, treated by acetone extraction and high temperature calcination, respectively, still maintain uniform core–shell structure with desirable mesoporous silica shell. Therein, the meso-SiO₂@Fe₃O₄(E) microspheres possess a distinct pore size distribution in 1.8–3.0 nm with large specific surface area (468.6 m²/g) and pore volume (0.35 cm³/g). Noteworthily, the coating period of this ultrasonic-assisted method (40 min) is much shorter than that of the conventional method (12–24 h). The morphology of microspheres and the mesoporous structure of silica shell are significantly influenced by initial concentration of CTAB (C_CTAB), ultrasonic irradiation power (P) and ultrasonic irradiation time (t). The acceleration roles of ultrasonic irradiation take effect during the whole coating process of mesoporous silica shell, including hydrolysis-condensation process of TEOS, co-assembly of hydrolyzed precursors and CTAB, and deposition of silica oligomers. In addition, the use of ultrasonic irradiation is favorable for improving the homogeneity of silica shell and the monodispersity of meso-SiO₂@Fe₃O₄ microspheres.     

Development of perovskite and phase transition in lead cobalt niobate modified lead zirconate titanate system

Ferroelectric lead zirconate titanate–lead cobalt niobate ceramics with the formula (1 − x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Co_1/3Nb_2/3)O₃ where x = 0.0–0.5 were fabricated using a high temperature solid-state reaction method. The formation process, the structure and homogeneity of the obtained powders have been investigated by X-ray diffraction method as well as the simultaneous thermal analysis of both differential thermal analysis (DTA) and thermogravimetry analysis (TGA). It was observed that for the binary system (1 − x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Co_1/3Nb_2/3)O₃, the change in the calcination temperature is approximately linear with respect to the PCoN content in the range x = 0.0–0.5. In addition, X-ray diffraction indicated a phase transformation from a tetragonal to a pseudo-cubic phase when the fraction of PCoN was increased. The dielectric permittivity is remarkably increased by increasing PCoN concentration. The maximum value of remnant polarization P_r (25.3 μC/cm²) was obtained for the 0.5PZT–0.5PCoN ceramic.     

Photocatalytic reduction of carbon dioxide with water using InNbO4 catalyst with NiO and Co3O4 cocatalysts

InNbO₄ was prepared by the solid-state reaction method. Various cocatalysts were added on InNbO₄ by the incipient-wetness impregnation method. The effects of co-catalyst and pretreatment conditions on the photocatalytic activity of InNbO₄ for photoreduction of carbon dioxide were investigated. NiO–InNbO₄ and Co₃O₄–InNbO₄ were pretreated by reduction at 500 °C for 2 h and subsequent oxidation at 200 °C for 1 h. The catalysts were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and UV–vis diffuse reflectance spectroscopy. The characterization results of NiO–InNbO₄ catalysts after pretreatment showed the presence of highly crystalline NiO and monoclinic Nb₂O₅. NiO–InNbO₄ with reduction–oxidation pretreatment exhibited the highest activity due to the presence of core–shell type Ni⁰ and NiO on the surface and the presence of a small amount of Nb₂O₅ as a promoter.     

The studies on structural and thermal properties of delithiated LixNi1/3Co1/3Mn1/3O2 (0 < x ≤ 1) as a cathode material in lithium ion batteries

The structural and thermal properties of the delithiated Li_xNi_1/3Co_1/3Mn_1/3O₂ (0 < x ≤ 1) material have been investigated by using diffraction and thermoanalytical techniques such as XRD and TG-DSC methods. XRD result shows that the delithiated materials maintain the O3-type structure with defined stoichiometric number at the range of 0.24 < x ≤ 1, exhibiting good crystal structural stability. The cobalt and nickel ions in the delithiated materials change their valence state (i.e. Co³⁺ to Co⁴⁺ and Ni³⁺ to Ni⁴⁺) when x < 0.49; the irreversible changes of the transformation may affect the first cycle of charge–discharge efficiency of the materials. A comparison of the results of TG-DSC with TPD-MS shows that the irreversible change of oxygen species during the delithiation process of Li_xNi_1/3Co_1/3Mn_1/3O₂ have great influence on the structural and thermal stability and reversibility of the materials.     

Spectroscopic properties of Co2+: ZnAl2O4 nanocrystals in sol–gel derived glass–ceramics

Transparent glass–ceramics containing zinc–aluminum spinel (ZnAl₂O₄) nanocrystals doped with tetrahedrally coordinated Co²⁺ ions were obtained by the sol–gel method for the first time. The gels of composition SiO₂–Al₂O₃–ZnO–CoO were prepared at room temperature and heat-treated at temperature ranging 800–950 °C. When the gel samples were heated up to 900 °C, ZnAl₂O₄ nanocrystals were precipitated. Co²⁺ ions were located in tetrahedral sites in ZnAl₂O₄ nanocrystals. X-ray diffraction analysis shows that the crystallite sizes of ZnAl₂O₄ crystal become large with the heat-treatment temperature and time, and the crystallite diameter is in the range of 10–15 nm. The dependence of the absorption and emission spectra of the samples on heat-treatment temperature were presented. The difference in the luminescence between Co²⁺ doped glass–ceramic and Co²⁺ doped bulk crystal was analysed. The crystal field parameter D_q of 423 cm⁻¹ and the Racah parameters B of 773 cm⁻¹ and C of 3478.5 cm⁻¹ were calculated for tetrahedral Co²⁺ ions.     

Laser power influence on Raman spectra of ZnO(Co) nanoparticles

Influence of laser power on nanocrystalline samples of ZnO(Co) prepared by commonly used wet chemistry method followed by calcination was investigated. Previous confirmation of the existence of ZnO and Co₃O₄ phases was based on the X-ray diffraction measurements. Here we report the experimental spectra of non-resonant Raman scattering in the range between 100 cm⁻¹ and 1600 cm^–1, for a series of samples irradiated with four different laser power densities. The laser power density has different influence on relative intensity of peaks that belong to ZnO phase than on those corresponding to Co₃O₄ phase. Both peak types show characteristic broadening and red shift toward lower frequencies. The laser power densities used in our study did not cause thermal destruction in any of the investigated samples. Laser-induced local heating effects in samples caused formation of cobalt dimers on the surface of Co₃O₄.     

Effect of growth time of hydrothermally grown cobalt hydroxide carbonate on its supercapacitive performance

We present the time-dependent synthesis of cobalt hydroxide carbonate nanorods by hydrothermal method with a systematic increase of different parameters such as specific surface area and specific capacitance as a function of different synthesis time. Morphological characterization of the cobalt hydroxide carbonate nanorods were carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that variation of the time of reaction plays a crucial role in the transformation of samples’ morphology. Cobalt hydroxide carbonate nanorods synthesized with 12 h reaction time, which is the reaction just before the materials transforms into cobalt oxide under the same synthesis conditions exhibited the highest specific capacitance of 466 F g⁻¹ at a current density of 1 A g⁻¹ in 6 M KOH electrolyte and also showed excellent stability with ∼99% capacitance retention after 2000 cycles at a current density of 10 A g⁻¹. Based on the above results, the cobalt hydroxide carbonate nanorods show a considerable potential as electrodes materials for supercapacitor applications.     

Effect of Fe doping on the structural and gas sensing properties of ZnO porous microspheres

Fe-doped ZnO porous microspheres composed of nanosheets were prepared by a simple hydrothermal method combined with post-annealing, and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Brunauer–Emmett–Teller N₂ adsorption–desorption measurements and photoluminescence (PL) spectra. In this paper we report Fe doping induced modifications in the structural, photoluminescence and gas sensing behavior of ZnO porous microspheres. Our results show that the crystallite size decreases and specific surface area increases with the increase of Fe doping concentration. The PL spectra indicate that the 4 mol% Fe-doped ZnO has higher ratio of donor (V_O and Zn_i) to acceptor (V_Zn) than undoped ZnO. The 4 mol% Fe-doped ZnO sample shows the highest response value to ppb-level n-butanol at 300 °C, and the detected limit of n-butanol is below 10 ppb. In addition, the 4 mol% Fe -doped ZnO sample exhibits good selectivity to n-butanol. The superior sensing properties of the Fe-doped porous ZnO microspheres are contributed to higher donor defects contents combined with larger specific surface area.     

Template-free sonochemical synthesis of hierarchically porous NiO microsphere

A novel template-free sonochemical synthesis technique was used to prepare NiO microspheres combined with calcination of NiO_2.45C_0.74N_0.25H_2.90 precursor at 500 °C. The NiO microspheres samples were systematically investigated by the thermograviometric/differential scanning calorimetry (TG/DSC), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), fourier-transformed infrared spectroscopy (FT-IR), Brunnauer–Emmett–Teller (BET) nitrogen adsorption–desorption isotherms, laser particle size analyzer, and ultraviolet–visible spectroscopy (UV–Vis). The morphology of the precursor was retained even after the calcination process, and exhibited hierarchically porous sphericity. The morphology changed over the ultrasonic radiation time, and the shortest reaction time was 70 min, which was much less than 4 h for the mechanical stirring process. The mechanical stirring was difficult to form the complete hierarchically porous microsphere structure. The BET specific surface area and the median diameter of the hierarchically porous NiO microspheres were 103.20 m²/g and 3.436 μm, respectively. The synthesized NiO microspheres were mesoporous materials with a high fraction of macropores. The pores were resulted from the intergranular accumulation. The ultraviolet absorption spectrum showed a broad emission at the center of 475 nm, and the band gap energy was estimated to be 3.63 eV.     

Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal β-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid

Porous (Ce_0.5Zr_0.5)O₂ solid solutions were prepared by thermolysis (T = 285 °C) or sonolysis (20 kHz, I = 32 W cm⁻², P_ac = 0.46 W mL⁻¹, T = 200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4–6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and μ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce_0.5Zr_0.5)O₂ solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m² g⁻¹ depending on synthesis conditions. The use of Barrett–Joyner–Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce_0.5Zr_0.5)O₂ mixed oxides loaded with 1.5 %wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C.     

Sonochemical reactions with mesoporous alumina

Herein, we report the sonochemical reactions with MSU-X mesoporous alumina (m-Al₂O₃) in aqueous solutions. Sonication (f = 20 kHz, I = 30 W cm^?2, W_aq = 0.67 W mL^?1, T = 36–38 °C, Ar) causes significant acceleration of m-Al₂O₃ dissolution in the pH range of 4–11. Moreover, power ultrasound has a dramatic effect on the textural properties and phase composition of m-Al₂O₃. Short-time sonication at pH = 4 leads to the formation of nanorods and nanofibers of boehmite, AlO(OH). Prolonged ultrasonic treatment causes high aspect morphology transformation to aggregated nanosheets in weakly acid solutions or plated nanocrystals in alkaline solutions. Sonochemical products in alkaline medium are composed principally from boehmite and small amounts of bayerite, Al(OH)₃. Silent hydrolysis of m-Al₂O₃ yields boehmite at pH = 4 and bayerite at pH = 11. The effect of ultrasound on the textural properties of mesoporous alumina as well as on the transformation of nanosized bayerite to boehmite can be consistently attributed to the transient strong heating of the liquid shell surrounding the cavitation bubble which caused the chemical processes similar to those occurred during hydrothermal treatment.     

Cobalt oxide nanolayers on Pd(100): The thickness-dependent structural evolution

The growth of interface-stabilized cobalt oxide (CoO_x) nanolayers on Pd(100) has been investigated and their structures are reported as a function of coverage. Several different phases have been observed by LEED and STM experiments, and they have been characterized spectroscopically by photoemission and X-ray absorption. The data indicate that in the low coverage regime (up to Θ_Co ≈ 2–3 ML) rock-salt CoO type phases are formed (defective in the single layer regime, and stoichiometric in multilayers) with (100) or (111) termination. At higher coverage (Θ_Co ≈ 10–20 ML) spinel Co₃O₄(111) and CoO(100) layers have been detected, in ratios dependent on the preparation conditions. The observed structures are discussed in relation to similar structures reported recently for CoO_x films on Ir(100) [W. Meyer et al., J. Phys.: Condens. Matter 20 (2008) 265011].