Carbon dioxide capture using diaminoalkane-grafted MIL-101(Cr)s: Critical role of geometric configuration of loaded amines

Preventing the increase of CO2 content in the atmosphere is crucial to mitigating climate change. In this study, we investigated the adsorption of CO2 using isostructural Cr-based MOFs, MIL -101 and MIL -100, after grafting diaminoalkanes with various chain lengths to determine the effect of the geometric configuration of the amines and to develop a competitive adsorbent. The performance of CO2 adsorption (e.g., adsorption capacity, selectivity, and adsorption heat) over MIL -101 increased as the size of diaminoalkanes increased, topped with 1,4butanediamine, and declined with longer diaminoalkanes. The favorable contribution of grafted 1,4-butanediamine in increasing the performances in CO2 adsorption could be explained by the adequate size of the amines for the optimized configuration in the pore window of the MIL -101. However, interestingly, none of the MIL -100s grafted with diaminoalkanes showed a similar positive effect probably because of the smaller pore window of MIL -100 than that of MIL -101. To the best of our knowledge, this is the first study to demonstrate the importance of geometric configuration (or, the chain length of amines) in amine-grafted MOFs for the CO2 adsorption that follows the general mechanism that requires interactions between two uncoordinated amines for the formation of ammonium carbamates. Moreover, one of the modified MIL -101 grafted with 1,4-butanediamine exhibited remarkable performance in CO2 adsorption with 4.0 times the adsorption capacity of CO2 at 15 kPa and 20.6 times CO2/N2 selectivity (based on ideal adsorbed solution theory, at 100 kPa) compared to the virgin MIL -101.