RESUMO
Due to their distinct and tailorable internal cavity structures, zeolites serve as promising materials for efficient and specific gas separations such as the separation of /CO2 from N2. A subset of zeolite materials exhibits trapdoor behavior which can be exploited for particularly challenging separations, such as the separation of hydrogen, deuterium, and tritium for the nuclear industry. This study systematically delves into the influence of the chabazite (CHA) and merlinoite (MER) zeolite frameworks combined with different door-keeping cations (K+, Rb+, and Cs+) on the trapdoor separation behavior under a variety of thermal and gas conditions. Both CHA and MER frameworks were synthesized from the same parent Y-zeolite and studied using in situ X-ray diffraction as a function of increasing temperatures under 1 bar H2 exposures. This resulted in distinct thermal responses, with merlinoite zeolites exhibiting expansion and chabazite zeolites showing contraction of the crystal structure. Simultaneous thermal analysis (STA) and gas sorption techniques further demonstrated how the size of trapdoor cations restricts access to the internal porosities of the zeolite frameworks. These findings highlight that both the zeolite frameworks and the associated trapdoor cations dictate the thermal response and gas sorption behavior. Frameworks determine the crystalline geometry, the maximum porosities, and displacement of the cation in gas sorption, while associated cations directly affect the blockage of the functional sites and the thermal behavior of the frameworks. This work contributes new insights into the efficient design of zeolites for gas separation applications and highlights the significant role of the trapdoor mechanism.
RESUMO
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 H2. 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.
