Peter C. Eklund

Hydrogen Adsorption in Carbon Materials

Recent reports of very high, reversible adsorption of molecular hydrogen in pure nanotubes, alkali-doped graphite, and pure and alkali-doped graphite nanofibers (GNFs) have aroused tremendous interest in the research community, stimulating much experimental work and many theoretical calculations worldwide. The U.S. Department of Energy (DOE) Hydrogen Plan has seta standard for this discussion by providing a commercially significant benchmark for the amount of reversible hydrogen adsorption. This benchmark requires a system-weight efficiency (the ratio of stored H 2 weight to system weight) of 6.5-wt% hydrogen and a volumetric density of 63 kg H 2 /m. If the encouraging experimental reports (summarized in Table I) are reproducible, it may be possible to reach the goals of the DOE Hydrogen Plan. On the other hand, the community still awaits confirmation of these experimental results by workers in other laboratories. Of additional concern is the fact that theoretical calculations have been unable to identify adsorption mechanisms compatible with the requirements of the DOE Hydrogen Plan. An economical, safe, hydrogen-storage medium is a critically needed component of a hydrogen-fueled transportation system. Hydrogen storage in a carbon-based material offers further advantages associated with its low mass density. Furthermore, fuel cell technology involving the conversion of hydrogen into protons, or hydrogen and oxygen into electric current, is being vigorously researched for both transportation and small power-plant applications.

Transparent Boron-Doped Carbon Nanotube Films

We report results of studies on the sheet resistance and optical transmission of thin films of boron-doped single-walled carbon nanotubes (SWNTs). Boron doping was carried out by exposure of SWNTs to B 2O 3 and NH 3 at 900 degrees C and 1-3 atom % boron was found in the SWNT bundles via electron energy loss spectroscopy (EELS). Boron doping was found to downshift the positions of the optical absorption bands associated with the van Hove singularities (E 11 (s) E 22 (s) and E 11 (m)) by approximately 30 meV relative to their positions in acid-treated and annealed SWNTs. Raman spectroscopy, EELS, and optical data are consistent with the picture that a few atom % boron has been substituted for carbon in the sp (2) framework of SWNTs. Finally, our results show that boron doping does not significantly affect the optical transmittance in the visible region. However, boron doping lowers the sheet resistance by approximately 30% relative to pristine SWNT films from the same batch. Boron-doped SWNT may provide a better approach to touch-screen technology.

PHONONS IN SILICON NANOWIRES

Cubic silicon in bulk form has changed the modern landscape of electronics and electro-optics. The physical and chemical properties of Si are perhaps the best understood of any crystalline solid. It is therefore a crucial crystalline material to research and understand the possibilities for new devices at the nanoscale where quantum confinement phenomena drive the formation of new electronic and phonon states. In this chapter, we focus on phonon properties expected for “confined” Si in the form of nanowires. We review calculations of the phonon dispersion in small diameter nanowires as well as experiments that seek to probe the change in the phonon dispersion and the associated physical properties. Discussion is presented on the observation and interpretation of data on inelastic light scattering from nanowire phonons (Raman and Brillouin Spectroscopy), thermal conductivity and specific heat.

Closeout of Advanced Boron and Metal Loaded High Porosity Carbons.

The Penn State effort explored the development of new high-surface-area materials for hydrogen storage, materials that could offer enhancement in the hydrogen binding energy through a direct chemical modification of the framework in high specific-surface-area platforms. The team chemically substituted boron into the hexagonal sp2 carbon framework, dispersed metal atoms bound to the boro-carbon structure, and generated the theory of novel nanoscale geometries that can enhance storage through chemical frustration, sheet curvature, electron deficiency, large local fields and mixed hybridization states. New boro-carbon materials were synthesized by high temperature plasma, pyrolysis of boron-carbon precursor molecules, and post-synthesis modification of carbons. Hydrogen uptake has been assessed, and several promising leads have been identified, with the requirement to simultaneously optimize total surface area while maintaining the enhanced hydrogen binding energies already demonstrated.