Metal Microporous Aromatic Polymers with Improved Performance for Small Gas Storage

A novel metal‐doping strategy was developed for the construction of iron‐decorated microporous aromatic polymers with high small‐gas‐uptake capacities. Cost‐effective ferrocene‐functionalized microporous aromatic polymers (FMAPs) were constructed by a one‐step Friedel–Crafts reaction of ferrocene and s ‐triazine monomers. The introduction of ferrocene endows the microporous polymers with a regular and homogenous dispersion of iron, which avoids the slow reunion that is usually encountered in previously reported metal‐doping procedures, permitting a strong interaction between the porous solid and guest gases. Compared to ferrocene‐free analogues, FMAP‐1, which has a moderate BET surface area, shows good gas‐adsorption capabilities for H 2 (1.75 wt % at 77 K/1.0 bar), CH 4 (5.5 wt % at 298 K/25.0 bar), and CO 2 (16.9 wt % at 273 K/1.0 bar), as well as a remarkably high ideal adsorbed solution theory CO 2 /N 2 selectivity (107  v / v at 273 K/(0–1.0) bar), and high isosteric heats of adsorption of H 2 (16.9 kJ mol −1 ) and CO 2 (41.6 kJ mol −1 ).