Investigation of Corannulene for Molecular Hydrogen Storage via Computational Chemistry and Experimentation

Abstract

Molecular simulations for hydrogen physisorption with corannulene molecules arranged according to their crystal structure result in good agreement with the weight-percent hydrogen stored as determined experimentally employing a 3-g sample of highly crystalline corannulene at ambient temperatures and 72 bar of pressure. Calculated enthalpies of adsorption for corannulene/hydrogen molecular systems obtained from ab initio calculations which take into account electron correlation via second-order Möller-Plesset perturbation theory are in good agreement with literature experimental enthalpies of adsorption for activated carbons interacting with molecular hydrogen. Ab initio results also show that corannulene molecules arranged in a sandwich structure are important for approximately doubling the binding energy of corannulene interacting with molecular hydrogen through a cooperative interaction. To test the effects of finite temperatures and pressures, stack arrays were used as input for molecular dynamics simulations and indicate that physisorption mechanisms including van der Waals forces and dipole-induced dipole interactions may yield enhanced adsorption capacity in relation to other carbon-based materials. These results will be instrumental in identifying interlayer separations of an array of corannulene or related molecules that may provide a high weight percent of physisorbed hydrogen.

Buckybowls: Corannulene and Its Derivatives

“…Experimentally hydrogen uptake of 0.8 mass% was obtained at ambient temperature (298 K) under the hydrogen pressure of 72 bar, which agreed well with molecular dynamic calculation . Theoretical calculation predicted that hydrogen uptake depends strongly on the distances between corannulene molecules (inter‐layer distance, ILD, and inter‐molecular distance, IMD), in addition to temperature and gas pressure, as shown in Figure . With ILD of 0.8 nm, hydrogen uptake is expected to be 4 mass% at 300 K under 130 bar, and even 6 mass% under 200 bar.…”

“…Adsorption of hydrogen onto corannulene was theoretically studied by density functional theory (DFT) and molecular dynamic simulations, and also measured experimentally . Experimentally hydrogen uptake of 0.8 mass% was obtained at ambient temperature (298 K) under the hydrogen pressure of 72 bar, which agreed well with molecular dynamic calculation . Theoretical calculation predicted that hydrogen uptake depends strongly on the distances between corannulene molecules (inter‐layer distance, ILD, and inter‐molecular distance, IMD), in addition to temperature and gas pressure, as shown in Figure .…”

“…Adsorption of hydrogen onto corannulene was theoretically studied by density functional theory (DFT) and molecular dynamic simulations, and also measured experimentally . Experimentally hydrogen uptake of 0.8 mass% was obtained at ambient temperature (298 K) under the hydrogen pressure of 72 bar, which agreed well with molecular dynamic calculation .…”

“…Theoretical prediction of hydrogen uptake on corannulene as functions of temperature with different ILDs and a constant IMD of 1.10 nm. Reproduced with permission . Copyright 2006, American Chemical Society.…”

Infrared spectroscopy of ionized corannulene in the gas phase

“…Corannulene has been suggested to possess structural and electronic properties relevant to superconductivity. 2 Encapsulation of smaller molecules in the bowl-shaped geometry has turned attention to possible applications in hydrogen storage 3 and molecular recognition 4 with corannulene pincers. Moreover, the occurrence of corannulene in interstellar environments has been suggested and possibly plays a role a) Author to whom correspondence should be addressed.…”