Investigation of the Dynamic Behaviour of H₂ and D₂ in a Kinetic Quantum Sieving System

Porous organic cages (POCs) are nanoporous materials composed of discrete molecular units that have uniformly distributed functional pores. The intrinsic porosity of these structures can be tuned accurately at the nanoscale by altering the size of the porous molecules, particularly to an optimal size of 3.6 Å, to harness the kinetic quantum sieving effect. Previous research on POCs for isotope separation has predominantly centered on differences in the quantities of adsorbed isotopes. However, nuclear quantum effects also contribute significantly to the dynamics of the sorption process, offering additional opportunities for separating H₂ and D₂ at practical operational temperatures. In this study, our investigations into H₂ and D₂ sorption on POC samples revealed a higher uptake of D₂ compared to that of H₂ under identical conditions. We employed quasi-elastic neutron scattering to study the diffusion processes of D₂ and H₂ in the POCs across various temperature and pressure ranges. Additionally, neutron Compton scattering was utilized to measure the values of the nuclear zero-point energy of individual isotopic species in D₂ and H_2. The results indicate that the diffusion coefficient of D₂ is approximately one-sixth that of H₂ in the POC due to the nuclear quantum effect. Furthermore, the results reveal that at 77 K, D₂ has longer residence times compared to H₂ when moving from pore to pore. Consequently, using the kinetic difference of H₂ and D₂ in a porous POC system enables hydrogen isotope separation using a temperature or pressure swing system at around liquid nitrogen temperatures.