The highly thermally and chemically stable imidazole framework ZIF-8 samples were separately postmodified with amine groups by using N,N′-dimethylethylenediamine (MMEN) and N,N-dimethylaminoethylamine (MAEA), which had the same molecular formula but different structures. The modified ZIF-8 samples (ZIF-8@amine) were thoroughly characterized, including powder X-ray diffractometry, Fourier-transformed infrared spectroscopy, and physical adsorption at 77 K by nitrogen, thermogravimetric analysis, and photophysical characterization. Results showed that after modification, the Brunauer–Emmett–Teller surface area and total pore volume both increased, almost one time higher than those of the original ZIF-8 sample, and followed the order: ZIF-8-MMEN > ZIF-8-MAEA > ZIF-8. Furthermore, the N–H group was successfully grafted into the modified ZIF-8 samples. To examine the sensing properties of the modified ZIF-8@amine samples toward the breath biomarkers of lung cancer, five potential volatile organic compound biomarkers were used as analytes. ZIF-8-MMEN and ZIF-8-MAEA revealed a unique capacity for sensing hexanal, ethylbenzene, and 1-propanol with high efficiency and sensitivity. The three samples all did not show sensing ability toward styrene and isoprene. In addition, ZIF-8, ZIF-8-MMEN, and ZIF-8-MAEA all can sense hexanal with a detection limit as low as 1 ppb.
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 ( Q st ) on the MA-ZIF-8, MMEN-ZIF-8, and ED-ZIF-8 all becomes higher, while Q st 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.
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