Carbon Nanotubes Decorated with Coordination Polymers for Fluorescence Detection of Heavy-Metal Ions and Nitroaromatic Chemicals.

Abstract

Herein, [Nd(NO3)3(H2pzdca)] n (MA-1) was synthesized from a reaction of 2,3-pyrazinedicarboxylic acid [H2Pzdca] as an organic linker with salt of Nd(III) under solvothermal conditions. The detailed structural analysis for crystals was performed utilizing single-crystal X-ray diffraction (SCXRD). After that, the neodymium-based coordination polymer (MA-1) crystal was directly generated upon the surface of functionalized carbon nanotubes (F-CNTs) through bonds or affinity between F-CNTs and MA-1 via the solvothermal approach. Meanwhile, the existence of F-CNTs does not affect the production of MA-1 crystals. FT-IR, PXRD, SEM, TEM, and SCXRD studies were used to characterize the crystalline material, MA-1 and MA-1@CNT. To investigate the MA-1@CNT sensing properties, Pb(II), As(III), Cr(VI), and nitrobenzene (NB) were utilized as analytes. It is worth mentioning that MA-1@CNT developed as a susceptible sensor exhibits a fluorescence "turn-on" response for Pb(II) and As(III) ions, while a fluorescence "turn-off" response in the case of Cr(VI) and NB with significantly low limit of detection (LOD) values of 15.9 for Pb(II), 16.0 for As(III), 76.9 for Cr(VI), and 21.1 nM for NB, which are comparable with the lowest LOD available in the literature. Furthermore, MA-1@CNT could be conveniently regenerated and reused for at least three cycles by simply filtering and washing with water several times. The sensing mechanism is ascribed to the inner filter effect owing to the overlap between the emission and/or excitation bands of MA-1@CNT with the absorption bands of Cr(VI) and NB. In contrast, the fluorescence enhancement in the case of Pb(II) and As(III) could be correlated to the chelation-enhanced fluorescence phenomenon. These results indicate that MA-1@CNT is an ideal sensor for Pb(II), As(III), Cr(VI), and NB recognition.