Advancing metal ions detection with porphyrinic coordination organic framework optical sensors
摘要
The detection of metal ions such as Al3+, Cr3+, Fe3+, Pb2+, and Hg2+ is crucial due to their significant environmental and biologic impacts. While Fe3+ and Cr3+ are essential in trace amounts, Pb2+ and Hg2+ are highly toxic even at low concentrations, necessitating the development of rapid and sensitive detection methods. Based on this condition, a zinc porphyrin-based metal–organic framework (MOF), Chem_CUJ_MOF2, was synthesized via coordination polymerization of Fe2+ with Zn-metalated meso-tetra(p-carboxyphenyl)porphyrin (ZnTCPP). The resulting MOF was thoroughly characterized using UV–Visible spectroscopy, FTIR, PXRD, TGA, BET, and SEM–EDX analyses. Chem_CUJ_MOF2 exhibits strong fluorescence properties and acts as an efficient “turn-on” fluorescent probe for metal ion detection in aqueous media. The addition of trivalent ions (Al3+, Cr3+, and Fe3+) results in significant fluorescence enhancement, with up to a 23-fold increase for Cr3+ and ~ 13-fold increases for both Al3+ and Fe3+, demonstrating higher sensitivity toward M3+ ions compared to divalent ions (Pb2+ and Hg2+), which show relatively weaker responses. A linear relationship between relative intensity (I/I₀) at 607 nm and metal ion concentration was observed in the 5–25 μM range for Al3+, Cr3+, and Fe3+, with correlation coefficients (R2) of 0.9908, 0.9414, and 0.9818, respectively. The limits of detection (LOD) were found to be remarkably low, 1.41 nM for Al3+, 3.51 nM for Cr3+, and 1.91 nM for Fe3+ demonstrating the exceptional sensitivity of Chem_CUJ_MOF2. In addition to fluorescence sensing, UV–Visible studies revealed similar spectral profiles for all tested metal ions with only minor variations in absorbance intensity. However, a distinct visual color change was observed exclusively in the presence of Fe3+, indicating a limited but noticeable colorimetric response. These results highlight the potential of Chem_CUJ_MOF2 as a high-performance “turn-on” fluorescent sensor for the rapid and quantitative detection of trivalent metal ions in environmental and analytical applications.