ABSTRACT
Lanthanide metal-organic frameworks (Ln-MOFs) broaden the optical sensing applications of lanthanide ions due to the antenna effect between organic ligands and metals. However, the sensitization ability of the ligand to metal ions is limited, and maximizing the sensitization of the electrochemiluminescence behavior of Eu3+ is still a challenge for the application of Ln-MOFs. Therefore, under the guidance of the "cascade sensitization mechanism" based on the antenna effect sensitizing the electrochemiluminescence of bimetallic Ln-MOFs, we proposed Eu/Tb-MOFs with high luminescence intensity as a signal probe. According to the antenna effect, the conjugated structure and high extinction coefficient of the benzene ring of 2-amino terephthalic acid (NH2-BDC) can enhance the ECL luminescence intensity of Eu/Tb-MOFs. Tb3+ can act as an energy bridge between NH2-BDC and Eu3+, buffering the energy gap. The bimetallic sensitization is formed between Tb3+ and Eu3+, which can inhibit the reverse internal flow of energy and ensure the high luminous efficiency of Eu3+. In addition, the nanosphere mixed valence Fe3O4 as a co-reactant accelerator promotes the formation of transient free radical SO4â¢- through the valence change of Fe2+/Fe3+. The ECL immunosensor constructed by luminophores Eu/Tb-MOFs and nanosphere Fe3O4 provided a new explanation for the ECL self-luminous of Eu/Tb-MOFs.
ABSTRACT
Heavy metal ions (HMIs) seriously threaten human health even under trace conditions. Therefore, accurate, efficient and simultaneous detection of multiple HMIs is of great significance. Here, a strategy of "co-movement catalysis" based on photo-assisted electrochemical catalysis is proposed by constructing a flexible electrochemical sensor with CoFe2O4/CNS heterojunction-modified nickel foam as the working electrode for simultaneous detection of HMIs. Regarding photo-assisted catalysis, CoFe2O4/CNS nanocomposites formed a p-n type heterojunction, effectively separating photo-generated electron-hole pairs and reducing photo-generated carriers' recombination rate, leading to the catalytic reaction of photogenerated electrons and holes with HMIs and atoms to improve the efficiency of preconcentration and stripping, further amplifying the electrochemical signal. Regarding electrochemical catalysis, the CoFe2O4 spinel contains variable valence transition metal ions Fe2+/Fe3+ and Co2+/Co3+, which can reduce and oxidize HMIs circularly, further enhancing the sensor's sensitivity. The portable sensor based on "co-movement catalysis" exhibited sensitive detection performance. The linear range is 0.100-10.0 µM for Pb2+ and 1.00-10.0 µM for Cd2+, with the detection limit of 0.0310 µM for Pb2+ and 0.219 µM for Cd2+, respectively. The recovery rate of the sensor to natural water samples is between 96% and 105%, which proves its development potential in environmental monitoring.
