Enhanced CO2 Adsorption and Selectivity of CO2/N2 on Amine@ZIF-8 Materials

Abstract

The ZIF-8 crystals were successfully postsynthetically modified using methylamine (MA), ethylenediamine (ED), and N, N′-dimethylethylenediamine (MMEN) to improve their adsorption performance toward CO2. Results showed that, compared with the original ZIF-8, the BET specific surface area of MA-ZIF-8, MMEN-ZIF-8, and ED-ZIF-8 has increased by 118.2%, 92.0%, and 29.8%, respectively. In addition, their total pore volume increased separately by 130.8%, 100%, and 48.7%. The adsorption capacities of CO2 on the amine-modified ZIF-8 samples followed the order MA−ZIF−8>MMEN−ZIF−8>ED−ZIF−8>ZIF−8. The CO2 adsorption capacities at 298 K on MA-ZIF-8, MMEN-ZIF-8, and ED-ZIF-8 were increased by 118.2%, 90.2%, and 29.8%, respectively. What is more, the CO2/N2 selectivities calculated using an IAST model of the amine@ZIF-8 samples at 0.01 bar and 298 K were also significantly improved and followed the order MA−ZIF−8 31.4>ED−ZIF−8 25.1>MMEN−ZIF−8 14.1>ZIF−8 11.5, which increased by 173.0%, 121.4%, and 22.6%, respectively. The isosteric heat of CO2 adsorption (Qst) on the MA-ZIF-8, MMEN-ZIF-8, and ED-ZIF-8 all becomes higher, while Qst of N2 on these samples was slightly lower in comparison with that on the ZIF-8. Furthermore, after six recycle runs of gravimetric CO2 adsorption-desorption on MA-ZIF-8, the adsorption performance of CO2 is still very good, indicating that the MA-ZIF-8 sample has good regeneration performance and can be applied into industrial CO2 adsorption and separation.