Two Stable Cd-MOFs as Dual-Functional Materials with Luminescent Sensing of Antibiotics and Proton Conduction.

Abstract

Construction and investigation of dual-functional metal-organic frameworks (MOFs) with luminescent sensing and proton conduction provide widespread applications in clean energy and environmental monitoring fields. By selecting a phosphonic acid ligand 4-pyridyl-CH2N(CH2PO3H2)2 (H4L) and coligand 2,2'-biimidazole (H2biim), two cadmium-based MOFs [Cd1.5(HL)(H2biim)0.5] (1) and (H4biim)0.5·[Cd2(L)(H2biim)Cl] (2) with different structures and properties have been hydrothermally synthesized by controlling reaction temperature. Based on the excellent thermal and chemical stabilities, and good luminescent stabilities in water solution, 1 and 2 can serve as luminescent sensors of chloramphenicol (CAP) with different quenching constant (KSV) values and detection limits (LODs) in water, simulated environmental system, and real fish water system. Meanwhile, different sensing effects and possible sensing mechanisms are analyzed in detail. Moreover, 1 and 2 can also serve as good proton-conducting materials. The proton conductivities can reach up to 1.41 × 10-4 S cm-1 for 1 and 1.02 × 10-3 S cm-1 for 2 at 368 K and 95% relative humidity (RH). Among them, 2 shows better luminescent sensing and proton conduction performance than 1, which indicates that different crystal structures have a great impact on the properties of MOFs. Through the discussion of the relationship between structures and properties in detail, the possible reasons for the differences in properties are obtained, which can provide theoretical guidance for the rational design of this kind of dual-functional MOFs in the future.