Capturing volatile radionuclide iodine from nuclear and medical waste streams is an important environmental issue. In this work, we found that the 2,6-position hydrogen atoms of a BODIPY core undergo fast iodination with volatile iodine at room temperature. Inspired by our observation, two novel BODIPY-based conjugated porous polymers (CPPs) BDP-CPP-1 and BDP-CPP-2, and the reference compound NBDP-CPP, were prepared, which were designed and then synthesized via the Sonogashira cross-coupling reaction of 1,3,5-triethynyl-benzene (TEB) and dibromo-substituted derivatives. With the coexistence of the BODIPY units and plenty of triple bonds and phenyl rings that could adsorb iodine with high capacity and affinity, compounds BDP-CPP-1 and BDP-CPP-2 exhibited satisfactory iodine adsorption capacities of 2830 mg g−1 and 2230 mg g−1, respectively. Moreover, BDP-CPP-1 was shown to adsorb volatile iodine through a chemical mechanism involving the 2,6-position hydrogen atoms of the BODIPY core. Surprisingly, the active sites on the BODIPY units for a chemical iodination reaction were mostly eliminated as a result of the crosslinking of BODIPY units during the Sonogashira coupling reaction. The preliminary results demonstrated that the iodine uptake abilities, which are in the order of BDP-CPP-1 > BDP-CPP-2 > NBDP-CPP, are not only dependent on the surface area, but also on the BODIPY units. The BDP-CPPs show high thermal stability with a decomposition temperature of about 300 °C. In addition, the BDP-CPPs demonstrated remarkable recyclability. Due to the highly π-conjugated porous structure along with the high affinity for iodine molecules and iodination sites, some BODIPY-based CPPs may provide a feasible pathway to adsorb other volatile compounds.
15 November 2018 in ACS Applied Materials & Interfaces
New classes of nanoporous organic polymers based on 1,3,5-triazine units (NOP-1–6) were synthesized via a straightforward, methane-sulfonic acid-catalysed, cost-effective Friedel–Crafts reaction of 2,4,6-trichloro-1,3,5-triazine and tetrahedral building blocks. Among them, NOP-3 with a Brunauer–Emmet–Teller (BET) specific surface area up to 894 m2 g−1 and the total volume exceeding 0.41 m3 g−1 exhibits good hydrogen adsorption capacity (up to 1.14 wt% at 77 K/1.0 bar) and high carbon dioxide uptake (up to 11.03 wt% at 273 K/1.0 bar). Furthermore, it presents an effective selectivity for CO2 adsorption (NOP-6, CO2/N2 selectivity 38.7 at 273 K/1.0 bar), demonstrating potential applications in gas adsorption and separation.
Porous organic polymers (POPs), which are built from pure organic building blocks through strong covalent bonds, are intriguing platforms with multiple functionalities.