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.