SnO2-decorated multiwalled carbon nanotubes and Vulcan carbon through a sonochemical approach for supercapacitor applications

Multiwalled carbon nanotubes (MWCNTs) and Vulcan carbon (VC) decorated with SnO₂ nanoparticles were synthesized using a facile and versatile sonochemical procedure. The as-prepared nanocomposites were characterized by means of transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infra red spectroscopy. It was evidenced that SnO₂ nanoparticles were uniformly distributed on both carbon surfaces, tightly decorating the MWCNTs and VC. The electrochemical performance of the nanocomposites was evaluated by cyclic voltammetry and galvanostatic charge/discharge cycling. The as-synthesized SnO₂/MWCNTs nanocomposites show a higher capacity than the SnO₂/VC nanocomposites. Concretely, the SnO₂/MWCNTs electrodes exhibit a specific capacitance of 133.33 F g⁻¹, whereas SnO₂/VC electrodes exhibit a specific capacitance of 112.14 F g⁻¹ measured at 0.5 mA cm⁻² in 1 M Na₂SO₄.     

Electrochemical redox supercapacitors using PVdF-HFP based gel electrolytes and polypyrrole as conducting polymer electrode

Electrochemical redox supercapacitors have been fabricated using polymeric gel electrolytes polyvinylidene fluoride co-hexafluoropropylene (PVdF-HFP)–ethylene carbonate (EC)–propylene carbonate (PC)–MClO₄: M = Li, Na, (C₂H₅)₄N and electrochemically deposited polypyrrole as conducting polymer electrode. The performance of the capacitors have been characterized using a.c impedance spectroscopy, cyclic linear sweep voltammetry and galvanostatic charge–discharge techniques. The capacitors shows larger values of overall capacitance of about 14–25 mF cm^− 2 (equivalent to a single electrode specific capacitance of 78–137 F g^− 1 of polypyrrole), which corresponds to the energy density of 11–19 W h kg^− 1 and power density of 0.22–0.44 kW kg^− 1. The values of capacitance have been found to be almost stable up to 5000 cycles and even more. A comparison indicates that the capacitive behaviour and the capacitance values are not much affected with the size of cations of the salts incorporated in gel electrolytes, rather predominant role of anions is possible at the electrode–electrolyte interfaces. Furthermore the coulombic efficiencies of all the cells were found to be nearly 100% that is comparable to the liquid electrolytes based capacitors.     

Spray pyrolyzed NiO–C nanocomposite as an anode material for the lithium-ion battery with enhanced capacity retention

NiO–C nanocomposite was prepared by a spray pyrolysis method using a mixture of Ni(NO₃)₂ and citric acid solution at 600 °C. The microstructure and morphology of the NiO–C composite were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) mapping, and thermogravimetric analysis (TGA). The results showed that the NiO nanoparticles were surrounded by amorphous carbon. Electrochemical tests demonstrated that the NiO–C nanocomposites exhibited better capacity retention (382 mAh g^− 1 for 50 cycles) than that of pure NiO (141 mAh g^− 1 for 50 cycles), which was also prepared by spray pyrolysis using only Ni(NO₃)₂ as precursor. The enhanced capacity retention can be mainly attributed to the NiO–C composite structure, composed of NiO nanoparticles surrounded by carbon, which can accommodate the volume changes during charge–discharge and improve the electrical conductivity between the NiO nanoparticles.     

Morphologically controlled preparation of CuO nanostructures under ultrasound irradiation and their evaluation as pseudocapacitor materials

Various morphologies of copper oxide (CuO) nanostructures have been synthesized by controlling the reaction parameters in a sonochemical assisted method without using any templates or surfactants. The effect of reaction parameters including molar ratio of the reactants, reaction temperature, ultrasound exposure time, and annealing temperature on the composition and morphology of the product(s) has been investigated. The prepared samples have been characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDAX), and thermogravimetric analysis (TGA). It has been found that Cu₂(OH)₃NO₃ nanoplatelets are achieved in mild conditions which can be then converted to various morphologies of CuO nanostructures by either using high concentrations of OH⁻ (formation of nanorods), prolonging sonication irradiation (nanoparticles), or thermal treatment (nanospheres). Application of the prepared CuO nanostructures was evaluated as supercapacitive material in 1 M Na₂SO₄ solution using cyclic voltammetry (CV) in different potential scan rates ranging from 5 to 100 mV s⁻¹. The specific capacitance has been calculated using CV curves. It has been found that the pseudocapacitor performance of CuO can be tuned via employing morphologically controlled samples. Accordingly, the prolonged sonicated sample (nanoparticles) showed the high specific capacitance of 158 F.g⁻¹.     

Synthesis of MnO2 nanoparticles from sonochemical reduction of MnO4− in water under different pH conditions

MnO₂ was synthesized by sonochemical reduction of MnO₄⁻ in water under Ar atmosphere at 20 °C, where the effects of solution pH on the reduction of MnO₄⁻ were investigated. The obtained XRD results showed that poor crystallinity δ-MnO₂ was formed at pH 2.2, 6.0 and 9.3. When solution pH was increased from 2.2 to 9.3, the morphologies of δ-MnO₂ changed from aggregated sheet-like or needle-like structures to spherical nanoparticles and finally to cubic or polyhedron nanoparticles. After further irradiation, MnO₂ was readily reduced to Mn²⁺. It was confirmed that H₂O₂ and H atoms formed in the sonolysis of water acted as reductants for both reduction for MnO₄⁻ to MnO₂ and MnO₂ to Mn²⁺. The optimum irradiation time for the effective synthesis of MnO₂ was 13 min at pH 2.2, 9 min at pH 6.0, 8 min at pH 9.3, respectively.     

Synthesis of TiO2/WO3 nanoparticles via sonochemical approach for the photocatalytic degradation of methylene blue under visible light illumination

Through an ultrasound assisted method, TiO₂/WO₃ nanoparticles were synthesized at room temperature. The XRD pattern of as-prepared TiO₂/WO₃ nanoparticles matches well with that of pure monoclinic WO₃ and rutile TiO₂ nanoparticles. TEM images show that the prepared TiO₂/WO₃ nanoparticles consist of mixed square and hexagonal shape particles about 8–12 nm in diameter. The photocatalytic activity of TiO₂/WO₃ nanoparticles was tested for the degradation of a wastewater containing methylene blue (MB) under visible light illumination. The TiO₂/WO₃ nanoparticles exhibits a higher degradation rate constant (6.72 × 10⁻⁴ s⁻¹) than bare TiO₂ nanoparticles (1.72 × 10⁻⁴ s⁻¹) under similar experimental conditions.     

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.     

Controllable synthesis of layered Co–Ni hydroxide hierarchical structures for high-performance hybrid supercapacitors

A facile solvothermal method is developed for synthesizing layered Co–Ni hydroxide hierarchical structures by using hexamethylenetetramine (HMT) as alkaline reagent. The electrochemical measurements reveal that the specific capacitances of layered bimetallic (Co–Ni) hydroxides are generally superior to those of layered monometallic (Co, Ni) hydroxides. The as-prepared Co_0.5Ni_0.5 hydroxide hierarchical structures possesses the highest specific capacitance of 1767 F g⁻¹ at a galvanic current density of 1 A g⁻¹ and an outstanding specific capacitance retention of 87% after 1000 cycles. In comparison with the dispersed nanosheets of Co–Ni hydroxide, layered hydroxide hierarchical structures show much superior electrochemical performance. This study provides a promising method to construct hierarchical structures with controllable transition-metal compositions for enhancing the electrochemical performance in hybrid supercapacitors.     

Galvanostatically deposited Fe: MnO2 electrodes for supercapacitor application

The present investigation describes the addition of iron (Fe) in order to improve the supercapacitive properties of MnO₂ electrodes using galvanostatic mode. These amorphous worm like Fe: MnO₂ electrodes are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR) and wettability test. The supercapacitive properties of MnO₂ and Fe: MnO₂ electrodes are investigated using cyclic voltammetry, chronopotentiometry and impedance techniques. It is seen that the supercapacitance increases with increase in Fe doping concentration and achieved a maximum of 173 F g^?1 at 2 at% Fe doping. The maximum supercapacitance obtained is 218 F g^?1 for 2 at% Fe: MnO₂ electrode. This hydrous binary oxide exhibited ideal capacitive behavior with high reversibility and high pulse charge–discharge property between ?0.1 and +0.9 V/SCE in 1 M Na₂SO₄ electrolyte indicating a promising electrode material for electrochemical supercapacitors.     

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.     

Physical,electrochemical and supercapacitive properties of activated carbon pellets from pre-carbonized rubber wood sawdust by CO2 activation

The physical and electrochemical properties of the activated carbon pellet electrodes have been investigated. Activated carbon pellets were prepared from single step carbonization process of pre-carbonized rubber wood sawdust at a temperature of 800 °C that followed with a CO₂ activation process at temperature in the range of 700–1000 °C. The BET characterization on the sample found that the surface area of the carbon pellet increased with the increasing of the activation temperature. The optimum value was as high as 683.63 m² g⁻¹. The electrical conductivity was also found to increase linearly with the increasing of the activation temperature, namely from 0.0075 S cm⁻¹ to 0.0687 S cm⁻¹ for the activation temperature in the range of 700–1000 °C. The cyclic voltammetry characterization of the samples in aqueous solution of 1 M H₂SO₄ also found that the specific capacitance increased with the increasing of the activation temperature. Typical optimum value was shown by the sample activated at 900 °C with the specific capacitance was as high as 33.74 F g⁻¹ (scan rate 1 mV s⁻¹). The retained ratio was as high as 32.72%. The activated carbon pellet prepared from the rubber wood sawdust may found used in supercapacitor applications.     

Preparation of ZIF-8 membranes supported on macroporous carbon tubes via a dipcoating–rubbing method

In the present work, a new dipcoating–rubbing method (DCRM) was developed to seed the surface of a macroporous carbon tube with a mixture of graphite and ZIF-8 nanoparticles. A continuous and low-defect ZIF-8 membrane was well formed on the seeded carbon tube by solvothermal growth. The DCRM involved a two-step process including first dipcoating a thin layer of the composite of graphite and ZIF-8 nanoparticles on the carbon surface and then rubbing the layer to form a stable seed layer. The graphite in the composite acting as binding agent could have two functions: (1) anchoring the ZIF-8 seeds onto the carbon surface; (2) smoothing the coarse surface of the macroporous carbon tube, thus forming a high quality ZIF-8 membrane. The as-prepared membrane was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and single gas permeation and was proved to be continuous and low-defect. The ideal selectivity of H₂/CH₄ is 7.9 with a H₂ permeance of 7.15×10⁻⁸ mol Pa⁻¹ s⁻¹ m⁻², which is higher than its corresponding Knudsen diffusion value. We could therefore expect the ZIF-8 membrane supported on macroporous tubular carbon to achieve a high selectivity of H₂ over CH₄ through a molecular sieving effect.     

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.     

Hydrophilic polyaniline nanofibrous architecture using electrosynthesis method for supercapacitor application

An electrosynthesis process of hydrophilic polyaniline nanofiber electrode for electrochemical supercapacitor is described. The TGA–DTA study showed polyaniline thermally stable up to 323 K. Polyaniline nanofibers exhibit amorphous nature as confirmed from XRD study. Smooth interconnected fibers having diameter between 120–125 nm and length typically ranges between 400–500 nm observed from SEM and TEM analysis. Contact angle measurement indicated hydrophilic nature of polyaniline fibers. Optical study revealed the presence of direct band gap with energy 2.52 eV. The Hall effect measurement showed room temperature resistivity ∼3 × 10⁻⁴ Ω cm and Hall mobility 549.35 cm⁻²V⁻¹ s⁻¹_. The supercapacitive performance of nanofibrous polyaniline film tested in 1 M H₂SO₄ electrolyte and showed highest specific capacitance of 861 F g⁻¹ at the voltage scan rate of 10 mV/s.     

Trace determination of safranin O dye using ultrasound assisted dispersive solid-phase micro extraction: Artificial neural network-genetic algorithm and response surface methodology

In this study, ultrasound assisted dispersive solid-phase micro extraction combined with spectrophotometry (USA-DSPME-UV) method based on activated carbon modified with Fe₂O₃ nanoparticles (Fe₂O₃-NPs-AC) was developed for pre-concentration and determination of safranin O (SO). It is known that the efficiency of USA-DSPME-UV method may be affected by pH, amount of adsorbent, ultrasound time and eluent volume and the extent and magnitude of their contribution on response (in term of main and interaction part) was studied by using central composite design (CCD) and artificial neural network-genetic algorithms (ANN-GA). Accordingly by adjustment of experimental conditions suggested by ANN-GA at pH 6.5, 1.1 mg of adsorbent, 10 min ultrasound and 150 μL of eluent volume led to achievement of best operation performance like low LOD (6.3 ng mL⁻¹) and LOQ (17.5 ng mL⁻¹) in the range of 25–3500 ng mL⁻¹. In following stage, the SO content in real water and wastewater samples with recoveries between 93.27–99.41% with RSD lower than 3% was successfully determined.     

Graphene oxides and carbon nanotubes embedded in polyacrylonitrile-based carbon nanofibers used as electrodes for supercapacitor

This study investigates the use of graphene oxides (GOs) and carbon nanotubes (CNTs) embedded in polyacrylonitrile-based carbon nanofibers (GO–CNT/CNF) as electrodes for the supercapacitor. GO–CNT/CNF was prepared by electrospinning, and was subsequently stabilized and activated. The specific capacitance of GO–CNT/CNF is 120.5 F g⁻¹ in 0.5 M Na₂SO₄ electrolyte, which is higher than or comparable to the specific capacitances of carbon-based materials in neutral aqueous electrolyte, as prepared in this study. GO–CNT/CNF also exhibits a superior cycling stability, and 109% of the initial specific capacitance after 5000 cycles. The high capacitance of GO–CNT/CNF could be attributed to the edge planes and the functional groups of GO, the highly electrical conductivity of CNT, and the network structure of the electrode.     

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.     

High surface area monodispersed Fe3O4 nanoparticles alone and on physical exfoliated graphite for improved supercapacitors

Highly conductive, unsophisticated and easy to be obtained physical exfoliated graphite (PHG) supporting well dispersed magnetite, Fe₃O₄/PHG nanocomposite, has been prepared by a one-step chemical strategy and physico-chemical characterized. The nanocomposite, favoured by the a-polar nanoparticles (NPs) capping, results in a self-assembled monolayer of monodispersed Fe₃O₄, covering perfectly the hydrophobic surfaces of PHG. The nanocomposite as an electrode material was fabricated into a supercapacitor and characterized by cyclic voltammetry (CV) and galvanostatic charge–discharge measurements. It shows, after a suitable annealing, significant electrochemical properties (capacitance value of 787 F/g at 0.5 A g⁻¹ and a Fe₃O₄/PHG weight ratio of 0.31) and good cycling stability (retention 91% after 30,000 cycles). Highly monodispersed very fine Fe₃O₄ NPs, covered by organic chains, have been also synthesized. The high surface area Fe₃O₄ NPs, after washing to leave a low content of organic chains able to avoid aggregation without excessively affecting the electrical properties of the material, exhibit remarkable pseudocapacitive activities, including the highest specific capacitance over reported for Fe₃O₄ (300 F/g at 0.5 A g⁻¹).     

Influence of Cu doping on the microstructure,optical properties and photoluminescence features of Cd0.9Zn0.1S nanoparticles

Cd_0.9−xZn_0.1Cu_xS (0≤x≤0.06) nanoparticles were successfully synthesized by a conventional chemical co-precipitation method at room temperature. Crystalline phases and optical absorption of the nanoparticles have been studied by X-ray diffraction (XRD) and UV–visible spectrophotometer. XRD confirms the phase singularity of the synthesized material, which also confirmed the formation of Cd–Zn–Cu–S alloy nanocrystals rather than separate nucleation or phase formation. Elemental composition was examined by the energy dispersive X-ray analysis and the microstructure was examined by scanning electron microscope. The blue shift of absorption edge below Cu=2% is responsible for dominance of Cu⁺ while at higher Cu concentration dominated Cu²⁺, d–d transition may exist. It is suggested that the addition of third metal ion (Cu²⁺/Cu⁺) is an effective way to improve the optical property and stability of the Cd_0.9Zn_0.1S solid solutions. When Cu is introduced, stretching of Cd–Zn–Cu–S bond is shifted lower wave number side from 678 cm⁻¹ (Cu=0%) to 671 cm⁻¹ (Cu=6%) due to the presence of Cu in Cd–Zn–S lattice and also the size effect. The variation in blue band emission peak from 456 nm (∼2.72 eV) to 482 nm (∼2.58 eV) by Cu-doping is corresponding to the inter-band radiation combination of photo-generated electrons and holes. Intensity of red band emission centered at 656 nm significantly increased up to Cu=4%; beyond 4% it is decreased due to the quenching of Cu concentration.     

Biosynthesis of gold nanoparticles by Aspergillum sp. WL-Au for degradation of aromatic pollutants

A simple method for synthesis of gold nanoparticles (AuNPs) using Aspergillum sp. WL-Au was presented in this study. According to UV–vis spectra and transmission electron microscopy images, the shape and size of AuNPs were affected by different parameters, including buffer solution, pH, biomass and HAuCl₄ concentrations. Phosphate sodium buffer was more suitable for extracellular synthesis of AuNPs, and the optimal conditions for AuNPs synthesis were pH 7.0, biomass 100 mg/mL and HAuCl₄ 3 mM, leading to the production of spherical and pseudo-spherical nanoparticles. The biosynthesized AuNPs possessed excellent catalytic activities for the reduction of 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, o-nitroaniline and m-nitroaniline in the presence of NaBH₄, and the catalytic rate constants were calculated to be 6.3×10⁻³ s⁻¹, 5.5×10⁻³ s⁻¹, 10.6×10⁻³ s⁻¹, 8.4×10⁻³ s⁻¹ and 13.8×10⁻³ s⁻¹, respectively. The AuNPs were also able to catalyze the decolorization of various azo dyes (e.g. Cationic Red X-GRL, Acid Orange II and Acid scarlet GR) using NaBH₄ as the reductant, and the decolorization rates reached 91.0–96.4% within 7 min. The present study should provide a potential candidate for green synthesis of AuNPs, which could serve as efficient catalysts for aromatic pollutants degradation.