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Title: SISGR - Hydrogen Caged in Carbon-Exploration of Novel Carbon-Hydrogen Interactions

Hydrogen trapped in a carbon cage, captured through repulsive interactions, is a novel concept in hydrogen storage. Trapping hydrogen via repulsive interactions borrows an idea from macroscale hydrogen storage (i.e. compressed gas storage tanks) and reapplies these concepts on the nanoscale in specially designed molecular containers. Under extreme conditions of pressure, hydrogen solubility in carbon materials is expected to increase and carbon is expected to restructure to minimize volume via a mixed sp2/sp3 hydrogenated state. Thermodynamics dictate that pre-formed C-H structures will rearrange with increased pressure, yet the final carbon-hydrogen interactions may be dependent upon the mechanism by which hydrogen is introduced. Gas “trapping” is meant to denote gas present in a solid in a high density, adsorbed-like state, when the external pressure is much less than that necessary to provide a comparable fluid density. Trapping thus denotes a kinetically metastable state rather than thermodynamic equilibrium. This project probed mechanochemical means to polymerize select hydrocarbons in the presence of gases, in an attempt to form localized carbon cages that trap gases via repulsive interactions. Aromatic, polyaromatic, and hydroaromatic molecules expected to undergo cyclo-addition reactions were polymerized at high (~GPa) pressures to form extended hydrogenated amorphous carbon networks. Notably, aromatics withmore » a pre-existing internal free volume (such as Triptycene) appeared to retain an internal porosity upon application of pressure. However, a high photoluminescence background after polymerization precluded in situ identification of trapped gases. No spectroscopic evidence was found after depressurization that would be indicative of pockets of trapped gases in a localized high-pressure environment. Control studies suggested this measurement may be insensitive to gases at low pressure. Similarly, no spectral fingerprint was found for gas-imbued spherical carbon nanoshells, even after chemical “capping” of the gas-imbued nanoshells to limit gas diffusivity. Subsequently, spectral probes of gas vibrational modes adsorbed in various carbon nanostructures (including activated carbons, single-wall carbon nanotubes, polymers of intrinsic microporosity (PIMs), and UV-irradiated PIMs with decreased pore size) were found only at high pressure. The vibrational mode of the adsorbed film became perturbed in high density films, and the perturbation was sensitive to surface functional groups, pore size, and pore dimension. Experimental results were corroborated with first-principle modeling using density functional theory. Development of semi-empirical correlations that relate the spectral features to pore dimension, geometry, and chemical potential of the adsorbed film are on-going.« less
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  1. Pennsylvania State Univ., State College, PA (United States)
Publication Date:
OSTI Identifier:
DOE Contract Number:
Resource Type:
Technical Report
Research Org:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States