Reversibility of the l-cysteine/l-cystine redox process at physiological pH on graphite electrodes modified with coenzyme B12 and vitamin B12

We report on the electrocatalytic activity of immobilized coenzyme B₁₂ and vitamin B₁₂ (as aquocobalamin) for the electrooxidation of l-cysteine and their effects on the electrochemical reversibility of the l-cysteine/l-cystine redox couple, a crucial biological system. Cyclic voltammograms of coenzyme B₁₂ adsorbed on a graphite electrode show that upon the reductive elimination of the 5′-deoxyadenosyl group from the cobalt center, at approximately −1.1 V, the electrochemical response of the modified electrode becomes similar to that of aquocobalamin. The electrochemically pretreated coenzyme B₁₂ shows a high electrocatalytic activity for the electro-oxidation of l-cysteine at physiological pH that has never been observed before with the commonly used metallophthalocyanine catalysts. Also, its activity is slightly higher than that exhibited by aquocobalamin.     

Electrochemical reduction of 2,4-dinitrophenol on nanocomposite electrodes modified with mesoporous silica and poly(vitamin B1) films

Electrochemical reduction of 2,4-dinitrophenol was investigated on a glassy carbon electrode modified with a nanocomposite Santa Barbara Amorphous silica (SBA-15) film and poly(vitamin B₁) film. For sensitive and selective detections, vanadium pentoxide and cerium oxide nanoparticles were incorporated into the matrix of SBA-15. 2,4-Dinitrophenol was reduced on the modified electrode at −0.39 and −0.25 V, corresponding to the reduction of 4-dinitrophenol and 2-dinitrophenol, respectively. Both cathodic peak currents were controlled by the diffusion of 2,4-dinitrophenol. The amplitude of the peak currents was proportional to the 2,4-dinitrophenol concentration in the range of 3.0–30 μM. The modified electrode demonstrated a long lifetime for the detection of 2,4-dinitrophenol. The detection limit of 2,4-dinitrophenol was 0.5 μM. Moreover, the modified electrode was used successfully to detect 2,4-dinitrophenol in lake water.     

Self-assembled monolayers of Vitamin B12 disulphide derivatives on gold

Using the self-assembly technique, novel monolayers on gold have been prepared from new cobyrinate dialkyl disulphide derivatives. The successful formation is proved by cyclic voltammetry and by in situ ellipsometry. The electrochemical characterisation by reductive desorption allows to estimate the surface coverage and reveals that the presence of two cobyrinates introduces some disorganisation in the monolayer. More packed and organised monolayers have been observed in systems containing only one terminal redox centre. From ellipsometric measurements a possible orientation of the cobyrinate centre in the adsorbed monolayer is modelled. The modified electrodes display electrocatalytic activity for the reduction of dissolved oxygen.     

Electro-oxidation of coal on NiO and/or Co3O4 modified TiO2/Pt electrodes

A TiO₂/Pt based electrode exhibited better activity for the oxidation of coal in a basic system compared to Ti/Pt, TiO₂–Cu/Pt and pure metal electrodes. The surface morphologies and composition of the electrodes were studied by SEM and XRD, respectively. Linear sweep voltammetry was employed to investigate the catalytic effects of electrodes, and the product of coal oxidization was determined by a gas collection test. The TiO₂/Pt electrodes that were modified with NiO and/or Co₃O₄ exhibited higher average currents and a lower decrease in mass during electrolysis compared to the other electrodes; this finding indicated that NiO and Co₃O₄ play important roles as catalysts.     

Pressureless sintering of B4C-TiB2 composites with Al additions

The effects of Al addition on pressureless-sintering of B₄C-TiB₂ composites were studied. Different amounts of Al from 0% to 5 wt.% were added to B₄C-TiB₂ mixtures (containing up to 30 wt.% TiB₂) and the samples were pressureless sintered at 2050 °C and 2150 °C under Ar atmosphere. Physical, microstructural and mechanical properties were analysed and correlated with TiB₂ and Al additions and sintering temperature. Addition of Al to B₄C-TiB₂ results in increased shrinkage upon sintering and final relative density and lower porosity, the effect is being more evident when both Al and TiB₂ are present. Fracture strength, elastic modulus and fracture toughness of 450 MPa, 500 GPa and 6.2 MPa.m^1/2, respectively were measured.     

Preparation of micro-dot electrodes of LiCoO2 and Li4Ti5O12 for lithium micro-batteries

Fabrications of micro-dot electrodes of LiCoO₂ and Li₄Ti₅O₁₂ on Au substrates were demonstrated using a sol-gel process combined with a micro-injection technology. A typical size of prepared dots was about 100 μm in diameter, and the dot population on the substrate was 2400 dots cm⁻². The prepared LiCoO₂ and Li₄Ti₅O₁₂ micro-dot electrodes were characterized with scanning electron microscopy, X-ray diffraction, micro-Raman spectroscopy, and cyclic voltammetry. The prepared LiCoO₂ and Li₄Ti₅O₁₂ micro-dot electrodes were evaluated in an organic electrolyte as cathode and anode for lithium micro-battery, respectively. The LiCoO₂ micro-dot electrode exhibited reversible electrochemical behavior in a potential range from 3.8 to 4.2 V versus Li/Li⁺, and the Li₄Ti₅O₁₂ micro-dot electrode showed sharp redox peaks at 1.5 V.     

Cycling-induced stress in lithium ion negative electrodes: LiAl/LiFePO4 and Li4Ti5O12/LiFePO4 cells

In this work, we examined the electrochemical behaviour of lithium ion batteries containing lithium iron phosphate as the positive electrode and systems based on Li-Al or Li-Ti-O as the negative electrode. These two systems differ in their potential versus the redox couple Li⁺/Li and in their morphological changes upon lithium insertion/deinsertion. Under relatively slow charge/discharge regimes, the lithium-aluminium alloys were found to deliver energies as high as 438 Wh kg⁻¹ but could withstand only a few cycles before crumbling, which precludes their use as negative electrodes. Negative electrodes consisting solely of aluminium performed even worse. However, an electrode made from a material with zero-strain associated to lithium introduction/removal such as a lithium titanate spinel exhibited good performance that was slightly dependent on the current rate used. The Li₄Ti₅O₁₂/LiFePO₄ cell provided capacities as high as 150 mAh g⁻¹ under C-rate in the 100th cycle.     

Synthesis and characterization of B13C2 boron carbide ceramic by pulsed electric current sintering

Approximately 400 nm grain sized boron-carbon ceramic was synthesized by the pulsed electric current sintering (PECS) method using boron and carbon powders. Relative density of up to 95% was achieved at sintering temperature of 1900 °C. This ceramic was composed with B₁₃C₂ as major phase and few B₄C and C, which were characterized by X-ray diffraction (XRD) and Rietveld refinement quantitative analysis and chemical analysis (CA) and electron probe microanalysis (EPMA). The microstructure was also observed via transmission electron microscope (TEM).     

Dielectric properties and microstructures of CaSiO3 ceramics with B2O3 addition

The effects of B₂O₃ additives on the sintering behavior, microstructure and dielectric properties of CaSiO₃ ceramics have been investigated. The B₂O₃ addition resulted in the emergence of CaO–B₂O₃–SiO₂ glass phase, which was advantageous to lower the synthesis temperature of CaSiO₃ crystal phase, and could effectively lower the densification temperature of CaSiO₃ ceramic to as low as 1100 °C. The 6 wt% B₂O₃-doped CaSiO₃ ceramic sintered at 1100 °C possessed good dielectric properties: _r = 6.84 and tan δ = 6.9 × 10⁻⁴ (1 MHz).     

Influence of H4SiW12O40 loading on hydrocracking activity of non-sulfide Ni-H4SiW12O40/SiO2 catalysts

The effect of H₄SiW₁₂O₄₀ loading on the catalytic performance of the reduced Ni-H₄SiW₁₂O₄₀/SiO₂ catalysts for hydrocracking of n-decane with or without the presence of thiophene and pyridine is studied. The catalysts were characterized by BET, XRD, Raman, XPS, H₂-TPR, H₂-TPD, NH₃-TPD and FT-IR of pyridine adsorption. It was found that addition of H₄SiW₁₂O₄₀ to the system increases the catalytic activity and the promoting effect is a function of the H₄SiW₁₂O₄₀ loading. The best result was obtained on 5%Ni-50%H₄SiW₁₂O₄₀/SiO₂ catalyst which shows the highest activity for hydrocracking of n-decane and excellent tolerance to the sulfur and nitrogen compounds in the feedstock. The results showed that a suitable amount of H₄SiW₁₂O₄₀ loading on the 5%Ni/SiO₂ catalyst increases the amount of both hydrogen adsorbed and Brønsted acid and Lewis acid sites on the catalyst. The high catalytic performance of the catalyst can be related to the nature of H₄SiW₁₂O₄₀ and the proper balance between metal and acid functions.     

Iron-enriched natural zeolite modified carbon paste electrode for H2O2 detection

This work demonstrates that iron-enriched natural zeolitic volcanic tuff (Paglisa deposit, Cluj county, Transilvania, Romania) resulting from a previous use as adsorbent in wastewater treatment can be recycled into effective electrode modifier applied to the electrocatalytic detection of hydrogen peroxide. After physico-chemical characterization of tuff samples using various techniques such as chemical analysis, X-ray diffraction, scanning electron microscopy, infrared spectroscopy, BET analysis and X-ray photoelectron spectroscopy, the electrochemical response of the iron-enriched zeolites was studied on the basis of solid carbon paste electrodes modified with these samples. The results indicate that iron centers in the zeolite are electroactive and that they act as electrocatalysts in the voltammetric and amperometric detection of H₂O₂. Best performance was achieved in phosphate buffer at pH 7, showing a sensitivity of 0.57 mA M⁻¹ cm⁻², a detection limit down to 60 μM, and a linear domain up to 100 mM H₂O₂.     

Preparation and microwave dielectric properties of 3ZnO·B2O3 ceramics with low sintering temperature

The preparation and dielectric properties of 3ZnO·B₂O₃ ceramics were investigated. Dense 3ZnO·B₂O₃ ceramics were obtained as sintered in the temperature range from 950 to 1000 °C for 3 h. The X-ray diffraction showed that the obtained ceramics were of a monoclinic 3ZnO·B₂O₃ structure. The ceramic specimens fired at 955 °C for 1 h exhibited excellent microwave dielectric properties: ?_r ∼ 6.9, Q × f ∼ 20,647 GHz (@6.35 GHz), and τ_f ∼ −80 ppm/°C. The dependences of relative density, ?_r, and Q × f of ceramics sintered at 955 °C on sintering soaking time showed that they all reached their plateaus as the soaking time was up to 60 min. Meanwhile, 3ZnO·B₂O₃ ceramics had no reaction with silver during cofiring, indicating it is a potential candidate for low-temperature cofired ceramic (LTCC) substrate.     

Synthesis of spinel Li4Ti5O12 anode material by a modified rheological phase reaction

Using lithium acetate dihydrate and tetra-n-butyl titanate as the raw materials, spinel Li₄Ti₅O₁₂ was successfully synthesized by a modified rheological phase method. Thermogravimetric analysis and differential scanning calorimetry (TG–DSC) of the thermal decomposition process of the precursor and X-ray diffraction (XRD) data indicate the crystallization of lithium titanates has occurred at 580 °C, and main phase Li₄Ti₅O₁₂ has obtained at 600 °C. Laser granulometer and scanning electron microscope (SEM) have been employed to estimate the particle size distribution, morphology and microstructure of the products. It reveals the prepared Li₄Ti₅O₁₂ powder had a small particle size (about 140 nm) and narrow size distribution (d_0.1 = 0.07, d_0.5 = 0.139, d_0.9 = 2.813 μm). Galvanostatic charge and discharge tests were carried out to characterize the electrochemical performances of Li₄Ti₅O₁₂. The result indicates that the Li₄Ti₅O₁₂ electrode material obtained from the precursor that had been experienced heat treatment at 110 °C exhibited discharge capacities of 161.6, 156.5 and 112.3 mAh g⁻¹ after 50 cycles at current rates 1, 2.5 and 10 C, respectively, demonstrating excellent high rate performance, due to the pure and well crystallized Li₄Ti₅O₁₂ with ultrafine particles and narrow size distribution.     

Characterization and electrochemical studies of Nafion/nano-TiO2 film modified electrodes

A nano-TiO₂ film from stable aqueous dispersion has been modified on a glassy carbon electrode (GCE), and was characterized by scanning electron microscopy (SEM) and surface-enhanced Raman spectroscopy (SERS). This nanostructured film exhibits an ability to improve the electron-transfer rate between electrode and dopamine (DA), and electrocatalyze the redox of DA. The electrocatalytical behavior of DA was examined by cyclic voltammetry (CV). Combined with Nafion, the bilayer-modified electrode (N/T/GCE) gives a sensitive voltammetric response of DA regardless of excess ascorbic acid (AA). Electrochemical impedance spectroscopy (EIS) at a fixed potential was performed at variously treated GCEs. The mechanism of the electrode reaction of DA at N/T/GCE and the equivalent circuits of different GCEs have been proposed.     

Detection of hydrazine based on Nano-Au deposited on Porous-TiO2 film

The fabrication of Nano-Au/Porous-TiO₂ composite modified glassy carbon electrode (GCE) and its application in the determination of hydrazine were proposed. The morphological characterization was examined by transmission electron microscope and scanning electron microscopy. The Nano-Au/Porous-TiO₂/GCE exhibited a wide linear range of hydrazine from 2.5 to 500 μM, with a detection limit of 0.5 μM at a signal-to-noise ratio of 3 and with a fast response time (within 3 s). Furthermore, the reaction mechanism of the hydrazine on the Nano-Au/Porous-TiO₂/GCE was explored. The ease of fabrication, high stability, and low cost of the modified electrode are the promising features of the proposed sensor.     

Preparation, characterization and dielectric properties of CaCu3Ti4O12 ceramics

CaCu₃Ti₄O₁₂ nano-sized powders were successfully prepared by sol-gel technique and calcination at 600-900 °C. The thermal decomposition process, phase structures and morphology of synthesized powders were characterized by IR, DSC-TG, XRD, TEM, respectively. It was found that the main weight-loss and decomposition of precursors occurred below 450 °C and the complex perovskite phase appeared when the calcination temperature was higher than 700 °C. Using above synthesized powders as starting materials, CCTO-based ceramics with excellent dielectric properties (?₂₅ = 5.9 × 10⁴, tan δ = 0.06 at 1.0 kHz) were prepared by sintering at 1125 °C. According to the results, a conduction mechanism was proposed to explain the origin of giant dielectric constant in CCTO system.     

Erosion behaviour of B4C-based ceramic composites

In this paper, TiO₂ was introduced into boron carbide and B₄C-based ceramic composites were obtained by uniaxial hot pressing. The mechanical properties, relative density and erosion behaviour of B₄C-based ceramic composites were investigated. X-ray analysis showed that the fabricated composites were composed of B₄C, TiB₂ and C phases. SEM technique was employed to observe the original polished surfaces and the eroded surfaces of B₄C-based ceramic composites. The effect of impingement angle, impact velocity of SiC erodent particle, relative density and phase ratio on the erosion rate of B₄C-based ceramic composites was determined. It was found that the erosion rate of B₄C-based ceramic composites increased with increasing of impingement angle and erodent particle velocity. The relative density and phase ratio influenced the erosion rate of B₄C-based ceramic composites significantly by influencing their mechanical properties.     

The viscosity reduction of nano-keggin-K3PMo12O40 in catalytic aquathermolysis of heavy oil

Nano-keggin-K₃PMo₁₂O₄₀ was synthesized, characterized by FT-IR, XRD and TEM, and then used in catalytic aquathermolysis of extra-heavy oil for the first time. The results evidently showed a viscosity reduction by 92.3% for the extra-heavy oil Zhen 411 at 280 °C, and by 80% and 90% in viscosity reduction for the extra-heavy oil G540 at 200 °C and 280 °C, with 9.25% and 11.69% in conversions of heavy to light content, respectively. To evaluate the performance, the structure and group composition of the heavy oil before and after the reaction were tested and analyzed by TLC-FID, FT-IR, GC-FID, ¹H NMR, EL and GC-MS. It was found that changes in oxygen-containing groups mainly happen during the catalytic aquathermolysis.     

Effect of particle dispersion on high rate performance of nano-sized Li4Ti5O12 anode

Nano-sized Li₄Ti₅O₁₂ powders with high dispersivity were fabricated by a sol-gel process using P123 as surfactant, which exhibited much better high rate performance towards Li⁺ insertion/extraction as compared to the densely aggregated Li₄Ti₅O₁₂ particles although the primary grain sizes of both samples were almost the same. The Li₄Ti₅O₁₂ electrode prepared from the well-dispersed nanopowders can preserve 88.6% of the capacity at 0.1 A g⁻¹ when being cycled at 1 A g⁻¹, which is obviously higher than that of the densely aggregated sample, in which only 30% capacity can be retained. By improving the dispersivity, the specific surface area of the Li₄Ti₅O₁₂ nanoparticles, hence the electrode-electrolyte contact area was increased; meanwhile, more homogeneous mixing of the active materials with carbon black was achieved. All these factors might have resulted in the better high rate performance.