Synthesis and structural investigation of new graphite intercalation compounds containing the perfluoroalkylsulfonate anions C10F21SO3, C2F5OC2F4SO3, and C2F5(C6F10)SO3

The preparation of graphite intercalation compounds (GIC’s) of three perfluorinated alkylsulfonate anions, C₁₀F₂₁SO₃⁻, C₂F₅OC₂F₄SO₃⁻ and C₂F₅(C₆F₁₀)SO₃⁻ is described for the first time. Pure stage 2 GIC’s are obtained by chemical oxidation of graphite with K₂MnF₆ in a solution containing hydrofluoric and nitric acids for 72 h. One-dimensional electron density maps derived from powder diffraction data are fit to obtain models for the intercalate interlayer regions (galleries) structures: the structure models provide details on anion concentrations, orientations, and conformations. In all cases, anion bilayers are observed with anion sulfonate headgroups oriented towards graphene sheets. Compared with structures calculated for the isolated anions, the intercalated anion conformations show changes in dihedral angles, involving rotations about C-C or C-O bonds. For the GIC containing C₂F₅(C₆F₁₀)SO₃⁻, the anion conformation change is related to the more efficient packing of anions in the intercalate gallery.     

Delamination, colloidal dispersion and reassembly of alkylamine intercalated graphite oxide in alcohols

Alkylamine intercalated graphite oxide delaminates to give colloidal dispersion in alcohols. Colloidal dispersion of the alkylamine intercalated GO increases with increase in chain length of the alcohols. The colloidal dispersions comprise of independent layers. The layers from these colloidal dispersions could be reassembled by evaporation or coagulation using acetone to form the parent layered solid. Layers from colloidal dispersions of two different alkylamine intercalated GO could be coassembled to get a solid in which the two different layers were stacked randomly. GO-bentonite composite could be obtained by a coassembly of layers from the colloidal dispersions of GO-amine and cetyl trimethyl ammonium intercalated bentonite.     

On the role of dihydrogen in the co-intercalation reactions into graphite of potassium and chalcogen

The influence of dihydrogen gas on the reactions between graphite and liquid potassium containing a very small amount of a chalcogen (O, S, Se, Te) was studied. The reactions were carried out under a pure argon atmosphere in a stainless steel reactor, between 400 and 600°C. Controlled amounts of dihydrogen gas can be added in this reactor. When dihydrogen is strictly absent, the co-intercalation of potassium and chalcogen does not take place at 400°C: only potassium intercalates, leading to the KC₈ binary compound. The same experiments carried out with controlled amounts of dihydrogen at the same temperature lead to various ternary compounds with oxygen, sulphur, selenium and tellurium. However, at 600°C, and strictly without dihydrogen, co-intercalation occurs, but only for S, Se and Te, allowing the preparation of new well-defined ternary graphite intercalation compounds. The co-intercalation of potassium and oxygen is possible only in the presence of dihydrogen, at any temperature.     

Preparation and characterization of silylated graphite oxide

Graphite oxide was silylated by various alkylchlorosilanes in the presence of butylamine and toluene, and new intercalation compounds were obtained. The silylating reagents with two or three chlorine atoms at silicon in them reacted with graphite oxide, while no reaction occurred when silylating reagents with only one chlorine atom was used. The silylating reagent mainly reacted with hydroxyl group of graphite oxide, forming Si-O bonding. The role of butylamine was not only exfoliating graphite oxide layer but also scavenging HCl molecule which caused the decomposition of silylated graphite oxide. The silicon content was almost constant ≈0.6 mol/graphite oxide for the samples silylated by alkyltrichlorosilane with shorter alkyl chain lengths. It increased with the increase of alkyl chain length and reached 1.7 mol/graphite oxide. The higher silicon content could be ascribed to further silylation on hydroxyl groups formed at silicon atoms of silylating reagent bonded to graphite oxide, bridging two silylating reagents.     

Characterizations of expanded graphite/polymer composites prepared by in situ polymerization

Poly(styrene-co-acrylonitrile)/expanded graphite composite sheets with very low in-plane (8.5 × 10⁻³ Ω cm) and through-thickness (1.2 × 10⁻² Ω cm) electrical resistivities have been prepared. The expanded graphite was made by oxidation of natural graphite flakes, followed by thermal expansion at 600 °C. Microscopic results disclosed that the expanded graphite has a legume-like structure, and each “legume” has a honeycomb sub-structure with many diamond-shaped pores. After soaking the expanded graphite with styrene and acrylonitrile monomers, the polymer/expanded graphite composite granules were obtained by in situ polymerization of the monomers inside the pores at 80 °C. The functional groups and microstructures of the oxidized graphite, expanded graphite and composites in the forms of particles or sheets were carefully characterized using various techniques, including X-ray powder diffraction, thermogravimetry, optical and electron microscopy. It was found that the honeycomb sub-structure survived after hot-pressing, resulting in a graphite network penetrating through the entire composite body, which produces a composite with excellent electrical conductivity.     

On the great difficulty of intercalating lithium with a second element into graphite

Lithium is able to intercalate into graphite leading to various binary graphite intercalation compounds, that are well defined by their stage. Concerning the ternaries, there is little literature on the subject. Thermodynamical and structural data, that differ largely from those of the other alkali metals, lead one to foresee some serious difficulties in synthesising such ternary compounds. Many experiments have attempted to synthesise ternary graphite intercalation compounds with lithium, using successively very electronegative elements, then fairly electronegative species and lastly electropositive metals. Numerous results, that are wholly negative, are described in this paper. The calcium-lithium system only allows one to prepare a novel intercalation compound, that is a first stage ternary phase exhibiting a large interplanar distance. This latter suggests that the intercalated sheets consist of several superimposed atomic layers. The synthesis of this ternary is not easy, because it needs reagents of very high purity. It possesses the brightness of metals and its strong hardness is very unusual among graphite intercalation compounds. On the other hand, the charge transfer between the graphene planes and the intercalated sheets, that just allows the intercalation, is especially high, and much higher than the LiC₆ compound.     

Theoretical study of stability of graphite intercalation compounds with Brønsted acids

The instability of acceptor graphite intercalation compounds (GICs) with Brønsted acids is a main obstacle to their extensive industrial use. Electron transfer from the solvated anion to the positively charged graphene layer is considered to be the first and rate-limiting step in the decomposition process, with the ionization potential of the intercalated anion being a measure of the stability of GICs. The effects of the hydrogen bonding and Coulomb interaction on the GIC stability are discussed.     

Catalytic removal of SO2, NO and HCl from incineration flue gas over activated carbon-supported metal oxides

Activated carbon-supported copper, iron, or vanadium oxide catalysts were exposed to incineration flue gas to investigate the simultaneous catalytic oxidation of sulfur dioxide/hydrogen chloride and selective catalytic reduction of nitrogen oxide by carbon monoxide. The results show that AC-supported catalysts exhibit higher activities for SO₂ and HCl oxidation than traditional γ-Al₂O₃-supported catalysts and the iron and vanadium catalysts act as catalysts instead of sorbents, and can decompose sulfate with evolution of SO₃ and then regenerate for more SO₂ adsorption to take place. The AC-supported catalysts also display a high activity for NO reduction with CO generated from a flue gas incineration process and the presence of SO₂ in the incineration flue gas can significantly promote catalytic activity. Using CO as the reducing agent for NO reduction is more effective than using NH₃, because NH₃ may be partially oxidized in the presence of excess O₂ (12 vol%. in the incineration flue gas used) to form N₂, which can decrease the overall extent of NO reduction.     

Electrochemical intercalation of aluminium chloride in graphite in the molten sodium chloroaluminate medium

Aluminium chloride intercalation in graphite was studied by anodic oxidation of compacted graphite (rod) and graphite powder electrodes in sodium chloroaluminate melt saturated with sodium chloride at 175 °C. The studies carried out by employing both galvanostatic and cyclic voltammetric techniques had shown that the intercalation reactions take place only beyond the chlorine evolution potential of +2.2 V vs. Al on both the electrodes. The extent of intercalation reaction was directly related to the anodic potential and probably to the amount of chlorine available on the graphite anodes. In the case of graphite powder electrode, a distinctly different redox process was observed at sub-chlorine evolution potentials and this was attributed to the adsorption of chlorine on its high surface area. This finding contradicts a report in the literature that the intercalation reactions occur at potentials below chlorine evolution in the chloroaluminate melt.     

Preparation and high temperature oxidation of SiC compositionally graded graphite coated with HfO2

SiC compositionally graded (SCG) graphite was coated with sol-gel-derived HfO₂ films and oxidized at 1500 °C in air. SCGed graphite was produced by reaction of graphite with molten Si at 1450 °C for 10 h. The sol-gel HfO₂ precursor solution was prepared by dissolving HfCl₄ in ethanol and refluxing with diethanol-amine and HNO₃, and was coated on SCGed graphite by dipping. The HfO₂-coated SCGed graphite was produced by decomposition of the precursor under conditions determined from the results of TG, DTA, and MS analysis. Oxidation of HfO₂-coated SCGed graphite was performed at 1500 °C in air, revealing a small weight loss (0.6 mg cm⁻²) after 15 h. It was found that HfO₂-coated SCGed graphite exhibits extremely high oxidation resistance, which may be due to the formation of HfSiO₄ acting to heal pores or cracks.