Thiophene-based porphyrin polymers for Mercury (II) efficient removal in aqueous solution

Development of novel sulf-functionalized porous organic polymers (POPs) for Mercury (II) (Hg²⁺) removal is of great significant, but the adsorbents always suffered by the low adsorption capacity, stability, and efficiency for the reason that the common construction of functionalized POPs from the functionalized monomers or post-functionalization of the POPs always sacrifice the porosity. In this paper, porphyrin-based POPs with different heteroatoms were constructed through the aldehyde monomer (benzene, 2,5-thiophenedicarboxaldehyde and thieno[3,2-b]thiophene-2,5-dicarboxaldehyde) and pyrrole according to the Adler-Longo method. In this way, nitrogen (N) in pyrrole and sulfur (S) in thiophene structures were embed into the backbone structure of the polymers. The functional structures not only act as the linking building block into the stable cross-linking structure, but also offer abundant uncovered functional sites for Hg²⁺ adsorption, resulting the porphyrin-based POPs high Hg²⁺ capacity (1049 mg/g), removal efficiency (more than 99.9%), good reusability and selectivity for its highest heteroatoms contents. The adsorption mechanism confirmed the cooperative coordination of N in porphyrin and S in thiophene with Hg²⁺. This work confirmed the functional groups play more important role in heavy metal adsorption, and the embedded functional sites into backbone also promotes the stability and the adsorption performance.