One-step fabrication of dual functional Tb³⁺ coordinated polymeric micro/nano-structures for Cr(VI) adsorption and...

Hexavalent chromium Cr(VI) has been considered as one of the most hazardous heavy metals because of its strong and persistent toxicity to the ecosystem and human beings. Herein, we have synthesized a double hydrophilic block co-polyarylene ether nitriles (abbreviated as dhPEN) bearing aromatic backbone as well as pendent carboxyl and sulfonate groups. Afterward, the synthesized dhPEN has been co-assembled with the lanthanide Tb³⁺ via a one-step solvent exchange protocol, leading to generation of Tb³⁺ coordinated dhPEN (Tb-dhPEN) micro/nano-structures that exhibit good adsorption capacity and detection sensitivity towards Cr(VI). More specifically, the direct self-assembly of dhPEN and Tb³⁺ in mixed H₂O/DMF solvents resulted to Tb-dhPEN microparticles with lamellar structures, which exhibited a high Cr(VI) adsorption capacity approaching to 402 mg/g. The detailed characterization confirm that Cr(VI) is adsorbed and partially reduced to Cr(III) by the Tb-dhPEN microparticles via chemical interaction. Furthermore, the self-assembly of dhPEN with Tb³⁺ in the H₂O/DMF mixed solvents containing NaOH contributed to the generation of spherical nanoparticles showing green emission at 545 nm, which can be selectively quenched by the Cr(VI), leading to the specific detection of trace concentration of Cr(VI) down to 0.12 nM as well as reliable determination of Cr(VI) presented in real environmental samples.