A Highly Proton-Conductive 3D Ionic Cadmium–Organic Framework for Ammonia and Amines Impedance Sensing

Abstract

Lately, the progressive study of metal-organic frameworks (MOFs) for the detection of ammonia and amines has made infusive achievements. Nevertheless, the investigation of proton-conductive MOFs used to detect the low concentrations of ammonia and amine gases at different relative humidities (RHs) at room temperature is relatively restricted. Herein, by solvothermal reaction of Cd(NO₃)₂ with 2-methyl-1 H-imidazole-4,5-dicarboxylic acid (H₃MIDC), a three-dimensional ionic MOF {Na[Cd(MIDC)]} _n (1) bearing ordered one-dimensional channels was successfully synthesized. Our research indicates that the uncoordination carboxylate sites are beneficial to proton transfer and the recognition of ammonia and amine compounds. The optimized proton conductivity of 1 reaches a high value of 1.04 × 10^-3 S·cm^-1 (100 °C, 98% RH). The room temperature sensing properties of ammonia and amine gases were explored under 68, 85, and 98% RHs, respectively. Satisfactorily, the detection limits of MOF 1 toward ammonia, methylamine, dimethylamine, trimethylamine, and ethylamine are 0.05, 0.1, 0.5, 1, and 4 ppm, respectively, which is one of the best room-temperature sensors for ammonia among previous sensors based on proton-conductive MOFs. The proton conducting and sensing mechanisms were highlighted as well.