A robust eco-compatible microporous iron coordination polymer for CO2 capture

Iron(iii) carboxylate based metal organic frameworks (MOFs)/porous coordination polymers (PCPs) have sparked great interest owing to their high structural diversity and tunable porosity, excellent stability, tailored functionality and their scalability as well as green synthesis associated with their biocompatible and biodegradable character. Herein, we present a new robust Fe(iii) based PCP (labelled MIL-178(Fe)) built up from chains of corner sharing Fe octahedra interconnected by 1,2,4-benzene tricarboxylic acid, delimiting one dimensional narrow pore channels (pore diameter < 4.5 angstrom) decorated with polar groups (mu(2)-OH and -CO2H functions). These structural and chemical features are suitable for the selective adsorption of CO2. MIL-178(Fe) was synthesized following a simple and green protocol in water under near ambient conditions using non-toxic reactants, allowing the production of sub-micrometer sized MIL-178(Fe) particles in a large amount (30 g). As shown by single-gas isotherms and CO2/N-2 co-adsorption experiments as well as molecular simulations, this material exhibits a moderate CO2 capacity at low pressure but a high CO2/N-2 selectivity. This is fully consistent with the presence of mu(2)-OH groups acting as CO2 adsorption sites, as revealed from both molecular simulations and in situ PXRD experiments. Finally, the good compatibility of this MOF with the elastomer block copolymer Pebax (R)-3533 allowed the processing of homogeneous and defect-free mixed matrix membranes with a MIL-178(Fe) loading of up to 25 wt% that outperformed pure Pebax (R)-3533 membranes for CO2/N-2 separation.

Automated summary

Iron(iii) carboxylate based metal organic frameworks (MOFs)/porous coordination polymers (PCPs) have attracted great interest due to their structural diversity, tunable porosity, stability, functionality, scalability, and green synthesis. This study presents a new Fe(iii) based PCP with one dimensional narrow pore channels decorated with polar groups, which shows moderate CO2 capacity and high CO2/N-2 selectivity. The compatibility of this MOF with elastomer block copolymer allows the production of mixed matrix membranes with improved CO2/N-2 separation performance.