Electrochemical properties of carbon-coated CaWO4 versus Li

Carbon-coated CaWO₄ nano-crystalline phases have been synthesized by ambient temperature solution precipitation method, characterized by X-ray diffraction, SEM and thermogravimetry and their electrochemical properties were studied versus Li metal. Galvanostatic cycling at a current of 60 mA/g in the voltage range 0.005-3.0 V on the 5 wt.% C-coated CaWO₄ gave a reversible capacity of 230 ± 5 mAh/g corresponding to 2.5 mol of Li, which is almost stable from 20 to 50 cycles. Under the same conditions, the 10 wt.% C-coated CaWO₄ showed a capacity of 355 ± 5 mAh/g (3.8 mol of Li) during the initial cycles, but the capacity degraded at a rate of 1.6 mAh/g per cycle in the range 5-100 cycles. A good operating voltage range was found to be 0.005-3.0 V with average discharge and charge potentials being 0.6 and 1.3 V, respectively. Coulombic efficiency in all cases was 96-98%. Cyclic voltammograms compliment the galvanostatic results. Impedance spectral data on the 10 wt.% C-coated CaWO₄ at different voltages during the first and 20th discharge-charge cycle have been interpreted in terms of the variations in the bulk and charge-transfer resistances of the composite electrode. A reaction mechanism involving the formation/decomposition of the oxide bronze, ‘Li_xWO_y’ has been proposed to explain the electrochemical cycling.     

Electrochemical insertion of lithium ions into disordered carbons derived from reduced graphite fluoride

Both covalent (obtained by direct fluorination at high temperature) and semi-ionic carbon fluorides (synthesized at room temperature) were reduced in order to obtain disordered carbons containing very small content of fluorine and different physical properties according to the reduction treatment (chemical, thermal or electrochemical). After a physical characterization (X-ray diffraction, electron spin resonance and FT-IR spectroscopies), the electrochemical behaviours of the pristine carbon fluorides and of the treated samples were investigated during the insertion of lithium using liquid carbonate-based electrolytes (LiClO₄-EC/PC, 50:50%, v/v). Both galvanostatic and voltammetric modes were performed and revealed that the voltage profiles and the capacities differed according to the starting material and the reduction treatment. Semi-ionic carbon fluoride treated in F₂ atmosphere for 2 h at 150 °C and then chemically reduced in KOH exhibits high reversible capacities (the reversible capacity is 530 mAh g⁻¹ in the second cycle); in this case, the voltage profiles show a large flat portion at potentials lower than 0.3 V which is attributed to the insertion/deinsertion of lithium ions between the small graphene sheets and/or the absorption of pseudo metallic lithium into the microporosity of the sample. Nevertheless, a part of the lithium ions are removed at potentials higher than 0.5 V versus Li⁺/Li limiting the useful capacity.     

Electrochemical insertion of sodium into hard carbons

The electrochemical insertion of sodium ions into different types of hard carbons was achieved in electrolytes composed of ethylene carbonate as the solvent and NaClO₄ as the salt. For all the materials studied the sodium uptake increases when the carbon highest heat treatment temperature (HTT) decreases. PAN-based carbon fibres appear to be suitable structures to allow significant sodium insertion. Thus, T650 ex-PAN fibres lead to a reversible capacity close to 209 mAh g⁻¹. In that case, sodium insertion occurs in two main ways: one is the adsorption on the single graphene layers and the other is the concomitant insertion into the porosity that occurs below 0.1 V versus Na⁺/Na. This second mechanism, which is indicated by a low-voltage plateau on the electrochemical curves, allows significant insertion. The compared electrochemical study of two saccharose-coke samples corresponding to different regions of Dahn's classification underlines the importance of the carbon precursor and of the manufacture process. The reversible capacity is equal to 184 mAh g⁻¹ for the sample heat treated at 800 °C which presents a high hydrogen content whereas it is close to 145 mAh g⁻¹ for the one characterized by a HTT of about 1500 °C and a low hydrogen content. The best electrochemical performances are obtained for pyrolyzed cellulose carbons. Indeed, the reversible capacity is about 279 mAh g⁻¹. Outgassing these carbons at 950 °C results in such a decrease of the reversible capacity down to 145 mAh g⁻¹. That can be related either to the thermal elimination of heteroelements or to modifications of the pore size distribution. Consequently, the most suitable hard carbon material for anodic applications in rechargeable sodium-ion batteries should both present a high residual hydrogen content and a significant microporosity.     

Acid-base reactions on model MgO surfaces

Three MgO surfaces of different structures have been employed as models for study of the acid-base properties of MgO. Surface spectroscopies including XPS, UPS, and ISS were used to determine the nature and the absolute coverage of surface intermediates, and the nature of bonding sites upon adsorption of Brønsted acid molecules on these surfaces. Different behavior patterns of the Brønsted acid molecules with varying strengths on the three model surfaces provide insights into the site requirements for dissociation of Brønsted acids on MgO. The base-catalyzed Cannizzaro reaction of formaldehyde was observed on these model surfaces under UHV conditions.     

A study on structure and electrochemical properties of (La, Ce, Pr, Nd)2MgNi9 hydrogen storage electrode alloys

(La, Ce, Pr, Nd)₂MgNi₉ hydrogen storage alloys were prepared through induction melting followed by a long annealing treatment. The structure and electrochemical properties of annealed alloys have been investigated by orthogonal design experiments. Both the individual effects of each substituting element and their interaction in alloys were studied systemically. It has been shown that the structure of main phase in alloys belongs to PuNi₃-type with a space group R-3m. Substituting rare-earth elements have a significant effect on both the phase structure of alloys and microstructure. The anisotropic change in the crystal structure of alloys can cause the acceleration of pulverization of alloy particles and result in the deterioration of the cyclic stability of alloy electrodes. Misch metals can raise the plateau pressure of hydrogen absorption/desorption. The discharge capacity of alloy ranges from 342.97 to 380.68 mAh g⁻¹ depending on the sort and content of substituting elements. Both cerium and neodymium can obviously reduce the discharge capacity of alloy electrodes. When compared to the La₂MgNi₉ alloy electrode, mish metals can significantly improve the high rate dischargeability of alloy electrodes. The improvement of the kinetic characteristic of alloy electrodes mainly results from the increase of the hydrogen diffusion rate in alloy bulk.     

Hydrogen evolution during the oxidation of formaldehyde on Au:: The influence of single crystal structure and Tl-upd

Hydrogen evolution during formaldehyde oxidation in alkaline solution has been monitored by Differential Electrochemical Mass Spectrometry on Au(111) and polycrystalline gold. The current efficiency for hydrogen evolution increases with higher concentration and is in the same range on both, polycrystalline Au and Au(111) electrode. The onset potentials and half-wave potentials are higher on Au(111). Reaction orders for the faradaic current on the bare gold electrodes have been determined as 0.21 for higher and 0.76 for lower concentrations. Reaction orders for hydrogen evolution during formaldehyde oxidation are 1.4 times higher in each case. Tafel slopes in the range of 140-160 mV are found. This signifies that the first reaction step involving the formation of adsorbed hydrogen is largely determining the overall reaction rate. In the presence of thallium adlayers hydrogen evolution from formaldehyde oxidation is largely suppressed. On the thallium modified polycrystalline Au, formaldehyde oxidation is shifted for 100 mV to higher potentials where Tl is partially desorbed and hydroxide is coadsorbed on the modified surface. On thallium modified Au(111), a similar process takes place, but in the same potential region as the onset of formaldehyde oxidation on the bare surface and therefore the formaldehyde oxidation is only slightly shifted. Tafel slopes are decreased to 80 mV/dec in the presence of thallium. In the presence of adsorbed thallium, the first reaction step is in equilibrium, the coverage with adsorbed hydrogen is smaller and its recombination to H₂ is largely suppressed.     

Electrochemical and spectroscopic evidences of corrosion inhibition of bronze by a triazole derivative

The electrochemical behavior of the bronze (Cu-8Sn in wt%) was investigated in 3% NaCl aqueous solution, in presence and in absence of a corrosion inhibitor, the 3-phenyl-1,2,4-triazole-5-thione (PTS). The inhibiting effect of the PTS was evidenced for concentrations higher than 1 mM for the cathodic process whereas its effect was clearly seen with a concentration as low as 0.1 mM for the anodic process. A significant positive shift of the corrosion potential was also observed, and its inhibiting effect increased with both its concentration and the immersion time of the sample. From voltammetry and electrochemical impedance spectroscopy experiments, the inhibiting efficiency of the PTS was found to be in the 94-99% range for 1 mM concentration. Scanning electron microscopy and X-ray energy dispersion analysis of the specimen surface show the presence of sulphur on the surface. Raman micro-spectrometry study confirms the protective effect of the PTS in aqueous solution through three types of interactions with the electrode, namely the adsorption of the inhibitor in a flat configuration, the formation of copper-thiol molecules, and when copper is released, the formation of a polymeric complex.     

使用毛细管电泳定量分析黑白显影液衰退反应中的对苯二酚和对苯二酚单磺酸盐

使用毛细管电泳分离并定量分析了对苯二酚——— 1种黑白显影液中的显影剂和它的衰退反应产物对苯二酚单磺酸盐。优化了的毛细管电泳分离。     

Induction plasma synthesis of fullerenes and nanotubes using carbon black–nickel particles

The existence of fullerenes (as allotropes of carbon) was established in the mid-1980s and during the last 15–18 years, systematic efforts have been devoted to improve the methods of their synthesis, including plasma-based system methods. The work presented here is focused on the investigation of fullerenes synthesis, using a radio frequency plasma reactor. The main objectives were to explore the use of induction plasma technology for the synthesis in-continuo of carbon fullerenes and to predict their formation conditions through conduct of theoretical studies. Thus, a thermodynamic study was carried out to predict the equilibrium composition of fullerenes produced at several combinations of operating conditions. Additionally, a statistical factorial design experiment, employing four factors at two levels, was also developed, in order to study the influence of the system’s operating parameters on the eventual C₆₀ fullerene yield. The results obtained showed that the reactor pressure, the electrical power and the raw material feed rates all have an important effect on the synthesis of fullerenes. The highest C₆₀ concentration in the products was found to be about 7.7 wt.%. Various other carbon nanostructures, such as nanotubes and nano-onions, were also successfully produced.     

Catalytic activities and properties of mesoporous sulfated Al2O3–ZrO2

Mesoporous sulfated Al₂O₃–ZrO₂ (MSAZ) catalysts with large surface areas and pore volumes after calcination at high temperature (650 °C) and with higher Al₂O₃ content than 20wt% were successfully prepared from a template of block copolymer (P84). The MSAZ catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption, transmission electron microscopy (TEM), ²⁷Al magic-angle spinning nuclear magnetic resonance (MAS NMR), thermogravimetric analysis (TG–DTG), temperature-programmed desorption of ammonia (NH₃-TPD) and infrared spectra (IR) of adsorbed pyridine. It is shown that the resulting mesostructured sulfated Al₂O₃–ZrO₂ samples have a well-developed textural mesoporosity. The number of acid sites present on MSAZ catalysts is higher than that on conventional sulfated zirconia, and the former catalysts are more active than the latter one for various acid-catalyzed reactions.