Dual-Functional Manganese-Doped ZnO-MOF Hybrid Material with Enhanced Hydrolytic Stability: A Fluorescent Photoinduced Electron Transfer Sensor for the Ultraselective Detection of Acetic Acid and Chromium (VI).

Abstract

In recent years, the synthesis of metal-organic framework (MOF)─nanocomposites has received wide attention from the scientific fraternity due to the presence of a tunable hierarchical architecture and invasive versatility in applications. The present work focuses on the solvothermal synthesis of a novel hybrid MOF-nanocomposite through the impregnation of Mn-doped ZnO nanoparticles onto the matrix of a pioneer metal-organic framework that is composed of zinc metal connected with terephthalic acid linkers (MOF-5). The hierarchical arrangements of the prepared material were further assessed by Fourier-transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), high-resolution transmission electron microscopy (HR-TEM), UV-visible, photoluminescence (PL), and dynamic light scattering (DLS) measurements. The porosity analysis via nitrogen sorption measurements at 77 K showed that the material is porous with hierarchical micro-, wide micro-, and mesopores. The SAED pattern confirms the polycrystallinity of the material, which is in good agreement with the data obtained from PXRD analysis. Effective integration of Mn-doped ZnO onto the MOF structure was confirmed by XPS analysis, and the study further identified the oxidation state of the elements present. The synthesized analyte is an efficient fluorescent chemosensor for the detection of acetic acid, which can find further potential applications in intracellular imaging. Interestingly, the same compound also selectively detects the presence of Cr(VI) ions, thereby acting as a dual sensor, which finds applications in the sensing and removal of environmental contaminants. The material showed a sharp and intense emission at 569 nm at an excitation wavelength of 320 nm, and it exhibits high quenching efficiencies of 99.87 and 71.43% toward the sensing of μM level concentration of acetic acid and Cr2O72-, respectively. The highly efficient fluorescent sensing of pollutants, even at a shorter linear range, discarded the possibility of sensing the pollutants at higher concentration ranges. The Ksv value for the detection of acetic acid and Cr(VI) is found to be 3.7017 × 106 and 11.0324 × 106 M-1, respectively, which further confirms the higher sensing ability of the synthesized fluorophore. The mechanistic studies and density functional theory calculations of Mn-doped ZnO@MOF-5 reveal that photoinduced electron transfer plays a significant role in the turn-off response toward acetic acid and Cr2O72- ions. In the case of acetic acid, in addition to photoinduced electron transfer, hydrogen bonding interactions may also lead to fluorescence quenching. To the best of our knowledge, no precedent work has been reported for the sensing of acetic acid in the solution state. All other fluorescent sensing reports put forward the sensing and adsorption of acetic acid in the gaseous state, which makes this material a pioneer among others for the detection of acetic acid in the solution phase.