Highly Sensitive and Selective Detection of Uranyl Ions Based on a Tb3+-Functionalized MOF via Competitive Host–Guest Coordination

Owing to the rapid development of the nuclear industry, uranium has become a global environmental contaminant due to its radiotoxicity and chemotoxicity, posing significant threats to human health and ecological safety. Although various instrumental and chemical analytical methods have been developed for uranyl ion detection in aquatic environments, searching for new sensors with high stability, sensitivity, and selectivity remains a challenge. In this study, a luminescent Zr-based metal–organic framework (MOF), designated as Tb@UiO-66-(COOH)2, was successfully synthesized utilizing a postsynthetic exchange (PSE) method along with Tb3+ ion doping for uranyl ion detection. Interestingly, the presence of UO22+ ions causes a replacement of guest ions (Tb3+) in the sensor via a competitive host–guest interaction, leading to significant luminescence quenching. The attenuation of the luminescence intensity of Tb@UiO-66-(COOH)2 exhibits an excellent linear relationship with UO22+ ion concentrations within a wide range of 0–2.52 μM. Notably, Tb@UiO-66-(COOH)2 demonstrates an unprecedentedly high detection sensitivity (Ksv = 2.16 × 105 M–1) and an extremely low limit of detection (LOD) down to 8.03 nM (1.91 ppb) in deionized water. More importantly, Tb@UiO-66-(COOH)2 can achieve high selectivity and efficient detection performance, even in the presence of significant excesses of competing ions. The values of Ksv were determined to be 2.10 × 105 M–1 in Xie'ao Lake water and 3.05 × 105 M–1 in seawater; the values of LOD were determined to be 8.26 nM (1.96 ppb) in Xie'ao Lake water and 5.68 nM (1.35 ppb) in seawater. To the best of our knowledge, this is the first instance of introducing a competitive host–guest coordination strategy into a MOF-based chemical sensor to achieve high-performance uranyl ion detection. Hence, the present work offers a novel idea for building functional MOFs for uranyl ion detection in aqueous solutions.