Highly Efficient Dual-Color Luminophores for Sensitive and Selective Detection of Diclazepam Based on MOF/COF Bi-Mesoporous Composites

Currently, studies on electrochemiluminescence (ECL) mainly focused on the single emission of luminophores while those on multi-color ECL were rarely reported. Here, a bi-mesoporous composite of the metal-organic framework (MOF)/covalent-organic framework (COF) with strong and stable dual-color ECL was prepared to construct a novel ECL sensor for sensitive detecting targets. A PTCA-COF with excellent ECL performance was loaded with a great amount of another ECL emitter Cu₃(HHTP)₂. Remarkably, the integrated composite had both ECL properties of PTCA-COF at 520 nm and Cu₃(HHTP)₂ at 600 nm wavelengths. Furthermore, Cu₃(HHTP)₂ with good electron transfer ability can greatly enhance the electrical conductivity and promote electrochemical activation. Thus, the simultaneous enhanced two-color ECL intensity and the catalytic properties of the conductive MOF exerted a dual enhancement effect on the ECL signal of the composite. Significantly, diclazepam can not only be adsorbed well on the multi-stage porous structure MOF/COF composite by π-π interactions but also selectively quench the ECL signal of the PTCA-COF, realizing the sensitive detection. The ECL sensor showed a wide detection range from 1.0 × 10^-13 to 1.0 × 10^-8 g/L, and the limit of detection (LOD) was as low as 2.6 × 10^-14 g/L (S/N = 3). The proposed ECL sensor preparation method was simple and sensitive, providing a new perspective for the potential application of multi-color ECL in the sensing field.