A dual-function Cd-MOF with high proton conduction and excellent fluorescence detection of pyridine

Abstract

Metal–organic frameworks have great potential in the field of proton conducting materials and fluorescent probes due to their structural tunability and designability. A novel water-stable metal organic framework material [Cd₂(Hdpb)(H₂O)₃] (Cd-MOF) was synthesized based on H₅dpb (H₅dpb = 3,5-diphosphonobenzoic acid) and Cd²⁺ ions. Cd²⁺ ions are connected with phosphonates and carboxyl groups of H₅dpb to form an infinitely extended 1D chain, which is further connected by the Hdpb⁴⁻ ligand and coordinated water to form a three-dimensional network structure. There are hydrogen bond networks in the 3D structure of the Cd-MOF, which are favorable for proton transfer, achieving its maximum proton conductivity of 2.97 × 10⁻³ S cm⁻¹ at 338 K and 98% relative humidity (RH). To realize its application in fuel cells, the Cd-MOF was introduced into the chitosan (CS) matrix, and a series of composite membranes (Cd-MOF@CS-X) with high proton conductivity were obtained. The results of AC impedance show that the proton conductivity of Cd-MOF@CS-5 reaches 3.55 × 10⁻¹ S cm⁻¹ at 358 K and 98% RH, which is comparable to the highest values reported for MOF-polymer complexes. Moreover, the Cd-MOF can be used as a selective fluorescent probe for pyridine detection, and its detection limit can reach 1.0 × 10⁻⁶ M. A bifunctional MOF with proton conduction and pyridine recognition is reported for the first time, and has important reference value for the practical application of functional MOFs in both electrochemical and luminescence sensing.