Combined hydrogen production and storage with subsequent carbon crystallization.

We provide evidence of low-temperature hydrogen evolution and possible hydrogen trapping in an anthracite coal derivative, formed via reactive ball milling with cyclohexene. No molecular hydrogen is added to the process. Raman-active molecular hydrogen vibrations are apparent in samples at atmospheric conditions (300 K, 1 bar) for samples prepared 1 year previously and stored in ambient air. Hydrogen evolves slowly at room temperature and is accelerated upon sample heating, with a first increase in hydrogen evolution occurring at approximately 60 degrees C. Subsequent chemical modification leads to the observation of crystalline carbons, including nanocrystalline diamond surrounded by graphene ribbons, other sp2-sp3 transition regions, purely graphitic regions, and a previously unidentified crystalline carbon form surrounded by amorphous carbon. The combined evidence for hydrogen trapping and carbon crystallization suggests hydrogen-induced crystallization of the amorphous carbon materials, as metastable hydrogenated carbons formed via the high-energy milling process rearrange into more thermodynamically stable carbon forms and molecular hydrogen.

Effect of expanded graphite lattice in exfoliated graphite nanofibers on hydrogen storage.

A graphite exfoliation technique, using intercalation of a concentrated sulfuric/nitric acid mixture followed by a thermal shock, has successfully exfoliated a herringbone graphite nanofiber (GNF). The exfoliated GNF retains the overall nanosized dimensions of the original GNF, with the exfoliation temperature determining the degree of induced defects, lattice expansion, and resulting microstructure. High-resolution transmission electron microscopy indicated that the fibers treated at an intermediate temperature of 700 degrees C for 2 min had dislocations in the graphitic structure and a 4% increase in graphitic lattice spacing to 3.5 A. The fibers treated at 1000 degrees C for 36 h were expanded along the fiber axis, with regular intervals of graphitic and amorphous regions ranging from 0.5 to >50 nm in width. The surface area of the starting material was increased from 47 m(2)/g to 67 m(2)/g for the 700- degrees C treatment and to 555 m(2)/g for the 1000- degrees C treatment. Hydrogen uptake measurements at 20 bar indicate that the overall hydrogen uptake and operative adsorption temperature are sensitive to the structural variations and graphitic spacing. The increased surface area after the 1000- degrees C treatment led to a 1.2% hydrogen uptake at 77 K and 20 bar, a 3-fold increase in hydrogen physisorption of the starting material. The uptake of the 700- degrees C-treated material had a 0.29% uptake at 300 K and 20 bar; although low, this was a 14-fold uptake over the starting material and higher than other commonly used pretreatment methods that were tested in parallel. These results suggest that selective exfoliation of a nanofiber is a means by which to control the relative binding energy of the hydrogen interaction with the carbon structure and thus vary the operative adsorption temperature.