RESUMEN
With the escalating prevalence of terrorism and global environmental pollution, nitroaromatic compounds (NACs) have increasingly come into focus as the primary culprit. To counter these challenges, it is imperative to develop simple and efficient methods for detecting NACs. Considering the electron-deficient structure of NAC molecules, this paper constructed a novel three-dimensional In-MOF with permanent porosity using electron-rich organic molecules 4'-[1,2,2-tris(3',5'-dicarboxy[1,1'-biphenyl]-4-yl)ethenyl]-[1,1'-biphenyl]-3,5-dicarboxylic acid (H8ETTB) for fluorescence detection by photoinduced electron transfer. The results indicated that In-ETTB can sensitively detect trace NACs in water. In-ETTB exhibited the best detection performance for 3-NP, achieving a Ksv value of 8.75 × 104 M-1 with a limit of detection of 0.27 µΜ in aqueous solution; this belongs to a relatively high level among the reported metal organic framework (MOF) materials. Subsequently, anti-interference experiments revealed that In-ETTB exhibits strong specificity fluorescence recognition of NACs, and it could still maintain its structural integrity and fluorescence emission intensity even after 7 cycles of testing. We confirmed that the fluorescence detection of NACs was due to a combined effect of competitive absorption and photoinduced electron transfer through experimental collaboration DFT calculations in detail. Meanwhile, the proton conductivity reached 2.45 × 10-2 S·cm-1 at 98% relative humidity and 90 °C, which is also a high level in MOFs. This work provides a universal method theoretical basis for designing NAC detectors with practical application prospects.
RESUMEN
Metal organic frameworks (MOFs) constructed with bismuth metal have not been widely reported, especially multifunctional Bi-MOFs. Therefore, developing multifunctional MOFs is of great significance due to the increasing requirements of materials. In this work, a 3D Bi-MOF (Bi-TCPE) with multifunctionality was successfully constructed, demonstrating high thermal stability, water stability, a porous structure, and strong blue fluorescence emission. We evaluated the properties of Bi-TCPE in detecting anions (S2-, Cr2O72-, and CrO42-) in aqueous solution, along with the rapid visual detection of H2S gas and proton conduction. In terms of anion detection, Bi-TCPE achieved the rapid detection of trace S2- in aqueous solutions, while the Ksv value was 1.224 × 104 M-1 with a limit of detection (LOD) value of 1.93 µM through titration experiments. Furthermore, Bi-TCPE could sensitively detect Cr2O72- and CrO42-, with Ksv values of 1.144 × 104 and 1.066 × 104 M-1, respectively, while LOD reached 2.07 and 2.18 µM. Subsequently, we conducted H2S gas detection experiments, and the results indicated that Bi-TCPE could selectively detect H2S gas at extremely low concentrations (2.08 ppm) and with a fast response time (<10 s). We also observed significant color changes under both UV light and sunlight. Therefore, we developed a H2S detection test paper for the rapid visual detection of H2S gas. Finally, we evaluated the proton conductivity of Bi-TCPE, and the experimental results showed that the proton conductivity of Bi-TCPE reached 4.77 × 10-2 S·cm-1 at 98% RH and 90 °C, achieving an excellent value for unmodified and encapsulated MOFs. In addition, Bi-TCPE showed high stability in proton conduction experiments (it remained stable after 21 consecutive days of testing and 12 cycles of testing), demonstrating relatively high application value. These results indicate that Bi-TCPE is a multifunctional MOF material with great application potential.