A symmetric carbon/carbon supercapacitor operating at 1.6 V by using a neutral aqueous solution

A high voltage symmetric carbon/carbon supercapacitor was built using a Na₂SO₄ aqueous solution. This system exhibits an excellent cycle life during thousands of cycles up to voltage values as high as 1.6 V. Three-electrode investigations show a particularly high potential window, ΔE = 2 V, for the considered activated carbon in Na₂SO₄. However, in a two-electrode cell, when the voltage is higher than 1.6 V, the potential of the positive electrode is beyond the oxidation potential of water, and AC is oxidized. These results demonstrate the potentialities of Na₂SO₄ for developing high energy density systems.     

Synthesis and characterization of the bimetallic polymers [MS4Ag2(Hmimt)2]n (where M = Mo or W,Hmimt = 1-methylimidazoline-2(3H)-thione): crystal structures of [WS4Ag2(Hmimt)2]n and [Ag2I2(Hmimt)]n

The title compounds were synthesized by the reactions of [NH₄]₂[MS₄] (M = Mo, W), AgI and Hmimt in acetone and characterized by IR, ¹H NMR and UV–Vis spectroscopy. The polymeric structure of [WS₄Ag₂(Hmimt)₂]_n was determined by X-ray crystallography. In this compound, there are two distinctly different coordination modes for the silver atoms. One Ag atom has a pseudo-tetrahedral geometry with one terminal monodentate-S Hmimt, two μ₂-S bridging Hmimt and one S atom of a monodentate WS₄ unit. The other is surrounded by four sulfur atoms belonging in pairs to two WS₄ fragments; the coordination geometry is distorted tetrahedral. The [WS₄Ag₂(Hmimt)₂]_n polymer represents the first example of tetrathiometalate anions [MS₄]²⁻ (M = Mo, W, or V) coordinated to another metal atom in a monodentate fashion. In both crystal structures determined the Hmimt ligands are present in the thione form, with coordination taking place via the sulfur atom only.     

Vanadium oxide-porous phosphate heterostructure catalysts for the selective oxidation of H2S to sulphur

Vanadium oxide–containing mesoporous materials, based on a surfactant expanded zirconium phosphate with silica galleries into the interlayer space, named porous phosphate heterostructure (PPH), were prepared by using TEOS and vanadium oxytripropoxide in n-propanol as sources of Si and V, respectively; with different Si/V molar ratios of 1, 2, 5 and 25; and calcining at 550 °C for 6 h. Using this method, vanadium can be partially incorporated to the structure of the gallery, but the surface area strongly decreases and the appearance of V₂O₅ crystallites increases when increasing the vanadium content. The catalysts were characterized by XRD, XPS, TEM, and Raman, and tested in the selective catalytic oxidation of H₂S using a fixed bed reactor, at atmospheric pressure, at 180–260 °C. The catalysts with high contents of vanadium are very active at 200 °C, showing H₂S conversions of 85–99%, with a high selectivity to elemental sulphur and with a low formation of SO₂. Accordingly V₂O₅ crystallites can be proposed as active and selective although the catalytic behavior is related to the number of accessible V-sites in the surface of the catalyst.     

Electrodeposited PbO2 thin film on Ti electrode for application in hybrid supercapacitor

PbO₂ thin films were prepared by pulse current technique on Ti substrate from Pb(NO₃)₂ plating solution. The hybrid supercapacitor was designed with PbO₂ thin film as positive electrode and activated carbon (AC) as negative electrode in the 5.3 M H₂SO₄ solution. Its electrochemical properties were determined by cyclic voltammetry (CV), charge–discharge test and electrochemical impedance spectroscopy (EIS). The results revealed that the PbO₂/AC hybrid supercapacitor exhibited large specific capacitance, high-power and stable cycle performance. In the potential range of 0.8–1.8 V, the hybrid supercapacitor can deliver a specific capacitance of 71.5 F g^?1 at a discharge current density of 200 mA g^?1(4 mA cm^?2) when the mass ratio of AC to PbO₂ was three, and after 4500 deep cycles, the specific capacitance remains at 64.4 F g^?1, or 32.2 Wh Kg^?1 in specific energy, and the capacity only fades 10% from its initial value.     

A Li3V2(PO4)3/C thin film with high rate capability as a cathode material for lithium-ion batteries

A monoclinic lithium vanadium phosphate (Li₃V₂(PO₄)₃) and carbon composite thin film (LVP/C) is prepared via electrostatic spray deposition. The film is studied with X-ray diffraction, scanning and transmission electron microscopy and galvanostatic cell cycling. The LVP/C film is composed of carbon-coated Li₃V₂(PO₄)₃ nanoparticles (50 nm) that are well distributed in a carbon matrix. In the voltage range of 3.0–4.3 V, it exhibits a reversible capacity of 118 mA h g^?1 and good capacity retention at the current rate of 1 C, while delivers 80 mA h g^?1 at 24 C. These results suggest a practical strategy to develop new cathode materials for high power lithium-ion batteries.     

Synthesis and structure of a bimetallic hybrid inorganic/organic layered coordination polymer with an octamolybdate cluster variant trapped between the α and δ isomeric forms

Hydrothermal combination of CuSO₄, MoO₃, and 4-phenylpyridine (4-phpyr) in a 1:4:4.5 ratio under basic conditions afforded purple crystals of {[Cu(4-phpyr)₄]₂(Mo₈O₂₆)·4-phpyr} (1), which were analyzed by spectroscopy and single crystal X-ray diffraction. The asymmetric octamolybdate clusters in 1 adopt an intermediate structural variant between the known α and δ isomeric forms, with four octahedral and three tetrahedral molybdenum coordination spheres, along with one molybdenum atom in a highly distorted square pyramidal environment. Paddle-wheel shaped [Cu(4-phpyr)₄]²⁺ cations link adjacent {α/δ-Mo₈O₂₆}⁴⁻ clusters into a 2-D layered rhomboid grid coordination polymer. Uncoordinated 4-phpyr molecules lie in incipient voids in the interlamellar regions. The structure of 1 illustrates the utility of sterically bulky coordination complexes in the stabilization of intermediate conformations during energetically facile polyoxometallate isomer interconversion. Crystallographic data: triclinic, P1, a = 13.717(3) Å, b = 13.728(3) Å, c = 14.809(3) Å, α = 109.251(4)°, β = 107.670(4)°, γ = 92.005(4)°, V = 2480.0(9) Å³, R₁ = 0.0637, wR₂ = 0.1054.     

Contribution enthalpic in the interaction of activated carbon with polar and apolar solvents

A method is presented for calculating the contribution that enthalpies make for every component of mixtures of activated carbon–water and activated carbon–hexane to the immersion enthalpy using the concepts that are used in the solution enthalpies. The immersion enthalpies of microporous activated carbon in water and in hexane have values from ?18.97 to ?27.21 and ?25.23 to ?47.89 J g^?1, respectively. From the immersion enthalpies and mass relation of the activated carbon in each of the solvents, the differential enthalpies are calculated for the activated carbon in water, Hw_DIFac, with values between ?15.95 and ?26.81 J g^?1, as are the differential enthalpies for the activated carbon in hexane, ΔHh_DIFac, with values between ?6.86 and ?46.97 J g^?1. For a low mass relation of the mixture components the contributions to the immersion enthalpy of the activated carbon and water differ by 3.20 J g^?1, while the difference between the contributions of the activated carbon and hexane is 19.41 J g^?1.     

Catalytic and kinetic spectrophotometric method for determination of vanadium(V) by 2,3,4-trihydroxyacetophenonephenylhydrazone

A new catalytic and kinetic spectrophotometric method for the determination of vanadium(V) was studied using 2,3,4-trihydroxyacetophenonephenylhydrazone (THAPPH) as an analytical reagent. The present method was developed on the catalytic effect of vanadium on oxidation of THAPPH by hydrogen peroxide in hydrochloric acid–potassium chloride buffer (pH = 2.8) at the 20th minute. The metal ion has formed 1:2 (M:L) complex with THAPPH. Beer’s law was obeyed in the range 20–120 ng/mL of V(V) at λ_max 390 nm. The sensitivity of the method was calculated in terms of molar absorptivity (1.999 × 10⁵ L mol⁻¹cm⁻¹) and Sandell’s sensitivity (0.000254 μg cm⁻²), shows that this method is more sensitive. The standard deviation (0.0022), relative standard deviation (0.56%), confidence limit (±0.0015) and standard error (0.0007) revealed that the developed method has more precision and accuracy. The stability constant was calculated with the help of Asmu’s (9.411 × 10⁻¹¹) and Edmond’s & Birnbaum’s (9.504 × 10⁻¹¹) methods at room temperature. The interfering effect of various cations and anions was also studied. The present method was successfully applied for the determination of vanadium(V) in environmental and alloy samples. The method’s validity was checked by comparing the results obtained with atomic-absorption spectrophotometry and also by evaluation of results using F-test.     

High oxygen-reduction activity of silk-derived activated carbon

Activated carbon prepared from silk fibroin, which is free of metal elements, showed a high catalytic activity for the oxygen-reduction reaction (ORR). The activated carbon had a very high onset potential of E_onset = 0.83 V (vs. RHE) in oxygen-saturated 0.5 M H₂SO₄ at 60 °C. The ORR on the activated carbon proceeded by a four-electron process in the high-electrode-potential region; this gradually decreased to a 3.5-electron reaction below about 0.6 V (vs. RHE). Only about 1% of nitrogen atoms (mostly quaternary) remained in the activated carbon by heat-treatment at up to 1200 °C are responsible for the high catalytic activity. The open circuit voltage of a polymer electrolyte fuel cell using the activated carbon as the cathode and a platinum/carbon black anode under pure oxygen and hydrogen gases, respectively, both at one atmosphere, was 0.96 V at 27 °C.     

Copper supported on porous activated carbon obtained by wetness impregnation: Effect of preparation conditions on the ozonation catalyst's characteristics

An activated carbon-supported copper heterogeneous catalyst based on (Cu/AC) was developed using a wetness impregnation process. The effect of preparation conditions on the catalyst's characteristics was examined. This work focuses on two key parameters: impregnation rate and calcination conditions (temperature and time). Catalysts were characterized by means of nitrogen sorptiometry at 77 K, Boehm analysis and pH_pzc analysis. It was found that the catalyst properties and the functional surface groups were affected by the operating conditions. The highest measured surface area, i.e. 1040 m²/g, was obtained for activated carbon (AC) impregnated with 12% of Cu loading after calcination at 550 °C for 2 h. The effect of adding copper on the surface of activated carbon on its adsorption capacity was also examined. The obtained results showed that after impregnation, the adsorption capacity of activated carbon was improved. Additionally, the performance of the Cu/AC catalyst on nitrobenzene ozonation was investigated. Our results show that the use of Cu/AC for heterogeneous catalytic ozonation enhanced significantly the degradation efficiency of nitrobenzene (NB) compared with simple ozonation and with ozonation catalyzed by AC without metal addition.     

Cyclometallated ruthenium(III) complexes: Synthesis,structure and properties

Reactions of Schiff bases (H₂apahR) derived from acetophenone and acid hydrazides, triethylamine and [Ru(PPh₃)₃Cl₂] (1:2:1 mole ratio) in methanol provide cyclometallated ruthenium(III) complexes of formula trans-[Ru(apahR)(PPh₃)₂Cl] in 74–81% yields. The complexes have been characterized by elemental analysis, magnetic susceptibility, spectroscopic (infrared, electronic and EPR) and electrochemical measurements. X-ray crystal structures of two representative complexes have been determined. In each complex, the metal centre is in distorted octahedral CNOClP₂ coordination sphere assembled by the C,N,O-donor meridionally spanning apahR^2?, the chloride and the two mutually trans-oriented PPh₃ molecules. All the complexes are one-electron paramagnetic (μ_eff. = 1.85–1.98 μ_B) and display rhombic EPR spectra in frozen (120 K) dichloromethane-toluene (1:1) solution. Electronic spectra of the complexes display several absorptions within 470–270 nm due to ligand-to-metal charge transfer and ligand centred transitions. The complexes are redox active and display a Ru(III) → Ru(II) reduction and a Ru(III) → Ru(IV) oxidation in the potential ranges ?0.66 to ?0.70 V and 0.75 to 0.80 V (vs. Ag/AgCl), respectively.     

NMR and theoretical study on interactions between diperoxovanadate complex and pyrazole-like ligands

To understand the effects of pyrazole substitution on reaction equilibrium, the interactions between a series of pyrazole-like ligands and [OV(O₂)₂(D₂O)]^?/[OV(O₂)₂(HOD)]^? were explored by using multinuclear (¹H, ¹³C, and ⁵¹V) magnetic resonance, HSQC, and variable temperature NMR in 0.15 mol/L NaCl ionic medium mimicking physiological conditions. These results show that the relative reactivities among the pyrazole-like ligands are 3-methyl-1H-pyrazole ≈ 4-methyl-1H-pyrazole ≈ 1H-pyrazole > 1-methyl-1H-pyrazole. As a result, the main factor which affects the reaction equilibrium is the steric effect instead of the electronic effect of the methyl group of these ligands. A pair of isomers has been formed resulting from the coordination of 3-methyl-1H-pyrazole and a vanadium complex, which is attributed to different types of coordination between the vanadium atom and the ligands. Thus, the competitive coordination leads to the formation of a series of six-coordinate peroxovanadate species [OV(O₂)₂L]^? (L, pyrazole-like ligands). Moreover, the results of density functional calculations provided a reasonable explanation on the relative reactivity of the pyrazole-like ligands as well as the important role of solvation in these reactions.     

Determination of formal potential of NADH/NAD+ redox couple and catalytic oxidation of NADH using poly(phenosafranin)-modified carbon electrodes

The electrochemical regeneration of NADH/NAD⁺ redox couple has been studied using poly(phenosafranin) (PPS)-modified carbon electrodes to evaluate the formal potential and catalytic rate constant for the oxidation of NADH. The PPS-modified electrodes were prepared by electropolymerization of phenosafranin onto different carbon substrates (glassy carbon (GC) and basal-plane pyrolytic graphite (BPPG)) in different electrolytic solutions. The formal potential was estimated to be ? 0.365 ± 0.002 V vs. SHE at pH 7.0. As for the bare carbon electrodes, the oxidation of NADH at the BPPG electrode was found to be enhanced compared with the GC electrode. For the PPS-modified electrodes, it was found that the electrocatalysis of PPS-modified electrodes for the oxidation of NADH largely depends on the carbon substrate and electrolyte solution employed for their preparation, i.e., the PPS-modified BPPG electrode prepared in 0.2 M NaClO₄/acetonitrile solution exhibits an excellent and persistent electrocatalytic property toward NADH oxidation in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of about 740 and 670 mV compared with those at the bare GC electrode and the PPS-modified GC electrode prepared in 0.2 M H₂SO₄ solution, respectively. A quantitative analysis of the electrocatalytic reaction based on rotating disk voltammetry gave the electrocatalytic reaction rate constants of the order of 10³–10⁴ M^?1 s^? 1 depending on the preparation conditions of the PPS-modified electrodes.     

Direct electrochemistry of single-stranded DNA on an ionic liquid modified carbon paste electrode

Electrochemical oxidation of thermally denatured single-stranded DNA (ssDNA) was studied on a room temperature ionic liquid N-butylpyridinium hexafluorophosphate (BPPF₆) modified carbon paste electrode (IL-CPE). A distinct oxidation peak appeared at +0.772 V (vs. SCE) on the IL-CPE after preconcentration of ssDNA at +0.35 V for 160 s in pH 7.0 phosphate buffer solution (PBS), which was attributed to the oxidation of guanine residue on the ssDNA molecular structure. The results showed an apparent negative shift of the oxidation peak potential and a great enhancement of the oxidation peak current on the IL-CPE compared with that of CPE. The electrochemical parameters of ssDNA on the IL-CPE were further calculated. Under the selected conditions, a linear calibration curve for ssDNA detection was obtained in the concentration range from 10.0 to 110.0 μg mL⁻¹ with the detection limit of 1.5 μg mL⁻¹(3σ).     

A Miniature glucose/O2 biofuel cell with single-walled carbon nanotubes-modified carbon fiber microelectrodes as the substrate

This study demonstrates a new kind of miniature glucose/O₂ biofuel cells (BFCs) based on carbon fiber microelectrodes (CFMEs) modified with single-walled carbon nanotubes (SWNTs). SWNTs are used as a support both for stably confining the electrocatalyst (i.e., methylene green, MG) for the oxidation of NADH and the anodic biocatalyst (i.e., NAD⁺-dependent glucose dehydrogenase, GDH) for the oxidation of glucose and for efficiently facilitating direct electrochemistry of the cathodic biocatalyst (i.e., laccase) for the O₂ reduction. The prepared micro-sized GDH-based bioanode and laccase-based biocathode exhibit good bioelectrocatalytic activity toward the oxidation of glucose and the reduction of oxygen, respectively. In 0.10 M phosphate buffer containing 10 mM NAD⁺ and 45 mM glucose under ambient air, the power density of the assembled miniature compartment-less glucose/O₂ BFC reaches 58 μW cm⁻² at 0.40 V. The stability of the miniature glucose/O₂ BFC is also evaluated.     

Esterification of acetic acid with n-Butanol using vanadium oxides supported on γ-alumina

Esterification of acetic acid with n-Butanol has been studied in a heterogeneous reaction system using two γ-alumina-supported vanadium oxide catalysts with different V loadings, which were prepared by the impregnation of a precipitated alumina. The alumina support and the supported catalysts were characterized using X-ray diffraction, N₂ adsorption, EDX analysis and NH₃-TPD techniques. The effects of the reaction time, of the molar ratio of the reactants, of the speed of agitation and of the mass fraction of the catalyst on the catalytic properties were studied. In the presence of the supported catalyst containing 10 wt % V₂O₅ (10V-Al₂O₃ sample) the conversion reached 87.7% after 210 min of reaction at 100 °C with an n-Butanol-to-acetic acid mole ratio equal to one. The conversion as well as the total acidity measured by TPD of NH₃ increased in the following order: Al₂O₃ < 5V-Al₂O₃ (5 wt % V₂O₅/Al₂O₃) < 10V-Al₂O₃. In all cases the reaction was completely selective to n-butyl acetate. Nevertheless, a loss in catalytic activity after three reaction cycles with 10 V₂O₅–Al₂O₃ catalyst was observed.     

An enzymatic glucose/O2 biofuel cell: Preparation,characterization and performance in serum

This study demonstrates a new kind of single-walled carbon nanotubes (SWNT)-based compartment-less glucose/O₂ biofuel cell (BFC) with glucose dehydrogenase (GDH) and bilirubin oxidase (BOD) as the anodic and cathodic biocatalysts, respectively, and with poly(brilliant creysl blue) (BCB) adsorbed onto SWNT nanocomposite as the electrocatalyst for the oxidation of NADH. The prepared GDH-polyBCB-SWNT bioanode exhibits an excellent electrocatalytic activity toward the oxidation of glucose biofuel; in 0.10 M phosphate buffer containing 20 mM NAD⁺ and 100 mM glucose, the oxidation of glucose commences at −0.25 V and the current reaches its maximum of 310 μA/cm² at −0.05 V vs. Ag/AgCl. At the BOD-SWNT biocathode, a high potential output is achieved for the reduction of O₂ due to the direct electron transfer property of BOD at the SWNTs. In 0.10 M phosphate buffer, the electrocatalytic reduction of O₂ is observed at a high potential of 0.53 V vs. Ag/AgCl with an electrocatalytic current plateau of ca. 28 μA/cm² at 0.45 V under ambient air and ca. 102 μA/cm² under O₂-saturated atmosphere. In 0.10 M phosphate buffer containing 10 mM NAD⁺ and 40 mM glucose under O₂-saturated atmosphere, the power density of the assembled SWNT-based glucose/O₂ BFC reaches 53.9 μW/cm² at 0.50 V. The performance and the stability of the glucose/O₂ BFC are also evaluated in serum. This study could offer a new route to the development of new kinds of enzymatic BFCs with a high performance and provide useful information on future studies on the enzymatic BFCs as in vivo power sources.     

Synthesis,characterization and fluorescence properties of hexanuclear zinc(II) complexes

Two hexanuclear zinc(II) complexes, [Zn₆(L¹)₂(μ₂-OH)₂(μ₂-CH₃COO)₈] · CH₃CN (1 · CH₃CN) and [Zn₆(L²)₂(μ₂-OH)₂(μ₂-CH₃COO)₈] · 4CH₃CN (2 · 4CH₃CN), where HL¹ = 4-methyl-2,6-bis(cyclohexylmethyliminomethyl)-phenol and HL² = 4-methyl-2,6-bis(1-naphthalylmethyliminomethyl)-phenol, have been synthesized and characterized by elemental analysis, FT-IR and fluorescence spectroscopic methods, and by X-ray diffraction analysis. In the asymmetric unit of complex 1, two of the three zinc atoms have pentacoordinate geometries and the other is tetrahedrally coordinated, whereas the three distinct Zn atoms in complex 2 adopt three different coordination environments, namely distorted octahedral, trigonal bipyramidal and tetrahedral. The fluorescence properties of the ligands and complexes have been investigated.     

New insights into the mechanism of flow-electrode capacitive deionization

We report on Faradaic reactions producing H⁺ (anode) and OH^– (cathode) in flow-electrode capacitive deionization (FCDI) operated at 1.2 V. These reactions underline an additional electrodialytical desalination mechanism within capacitive deionization, which proceeds in parallel to the known electrosorption mechanism. Examination of flow-electrodes (100 ml each, 5% (wt) activated carbon) during FCDI (121 cm² effective membrane area) of 150 ml, 4 g/l NaCl solution revealed that significant amounts of Na⁺ and Cl⁻ ions (up to 50% and 30% of Cl⁻ and Na⁺, respectively) were not adsorbed in the activated carbon particles but were rather dissolved in the aqueous phase of the flow-electrodes. Production of acid (resulting in pH ≈ 1.5) and base (pH ≈ 12.5) in the flow-anode and -cathode solutions was observed during the operation. Reverse pH behaviors were obtained during the regeneration of the flow-electrodes by potential reversal. pH neutralization of the flow-electrode solutions resulted in a sharp increase in both the desalination rate and the electric current of the FCDI cell. Reacting NaOH and HCl in a short-circuited FCDI cell resulted in NaCl production in the water compartment and pH neutralization of both flow-electrodes.Apparently reversible Faradaic reactions that occur on the flow electrodes in the FCDI can be dependent on the properties of the carbon material, electrolyte composition and applied operational parameters (e.g. cell potential) and need to be studied in further detailed investigations.     

Study on electrochemical performance of activated carbon in aqueous Li2SO4, Na2SO4 and K2SO4 electrolytes

The electrochemical performances of activated carbon (AC) in 0.5 mol/l Li₂SO₄, Na₂SO₄ and K₂SO₄ aqueous electrolytes were investigated. The cyclic voltammetric results at different scan rates show that the rate behaviors of AC in the three electrolytes improve in the order of Li₂SO₄ < Na₂SO₄ < K₂SO₄. This improvement can be mainly ascribed to the following two reasons: (1) the decreasing equivalent series resistance in the order of Li₂SO₄ > Na₂SO₄ > K₂SO₄, which is the main factor influencing the maximum output power, and (2) the increasing migration speed of hydrated ions in the bulk electrolyte and in the inner pores of AC electrode in the order of Li⁺ < Na⁺ < K⁺. Their cycling behaviors do not show any differences in capacitive fading. The above results provide valuable information to explore new hybrid supercapacitors.