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

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 (TbdhPEN) 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 TbdhPEN 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.

Automated summary

A double hydrophilic block co-polyarylene ether nitriles (dhPEN) with carboxyl and sulfonate groups was synthesized and co-assembled with lanthanide Tb3+ to form Tb3+ coordinated dhPEN (TbdhPEN) micro/nano-structures. The TbdhPEN exhibited high adsorption capacity for Cr(VI) and selective detection at trace concentrations, making it suitable for environmental sample analysis.