High-Pressure Sorption of Hydrogen in Urea.

Hydrogen sorption in urea C(NH2)2O has been probed by direct measurements in Sievert's apparatus at 7.23 and 11.12 MPa as well as by Raman spectroscopy for the sample compressed and heated in a high-pressure gas-loaded diamond-anvil cell up to 14 GPa. Both these methods consistently indicate the occurrence of small nonstoichiometric sorption of hydrogen in urea phase I. The compression of urea in hydrogen affects the Raman shifts of the C-N bending mode δ and the stretching mode υs. The sorption affects the H2 vibron position too. The sorption of 1.3 × 10-2 at 11.12 MPa corresponds to a stochastic distribution of H2 molecules in channel pores of urea. The mechanism leading to this stochastic sorption involves strong correlations between the swollen nanodot regions around the pores accommodating H2 molecules and the squeezed neighboring pores too narrow to act as possible sorption sites. This study on the hydrogen-bonded framework (HOF) of urea marks the smallest pores capable of absorbing hydrogen documented so far. This observation also reveals a new class of compounds, which is located between those that absorb large stoichiometric amounts of certain guest molecules and those that do not absorb them at all, namely, the group of compounds that absorb the guests in a stochastic manner.