Multifunctional Zr-MOF Based on Bisimidazole Tetracarboxylic Acid for pH Sensing and Photoreduction of Cr(VI)

Herein, a new luminescent zirconium MOF [Zr-BBI, BBI = 4,4',4″,4‴-(1,4-phenylenebis(1H-imidazole-2,4,5-triyl))tetrabenzoic acid] was successfully constructed by a rationally designed functionalized bisimidazole tetracarboxylic acid ligand. Zr-BBI consists of eight-connected Zr6 clusters and four-connected BBI ligands. The high connection mode must be responsible for the high stabilities of Zr-BBI in both acidic and basic systems. Apart from the high stability, the inherent bisimidazole units endow Zr-BBI with the traits of intense fluorescent emission as well as the protonation/deprotonation behavior. Therefore, Zr-BBI could display a highly sensitive fluorescence response along with the varying pH values in the aqueous solutions and act as a pH sensing scaffold, especially in the pH value range from 4.6 to 7.12. Zr-BBI also shows good fluorescence detection performance toward Cr2O72- at a low concentration with a high KSV value up to 6.49 × 104 M-1. Moreover, by the utilization of Zr-BBI as a catalyst, Cr(VI) could be effectively photoreduced to Cr(III) in aqueous solution under visible light irradiation, in which the introduction of a hole scavenger (benzyl alcohol) could further significantly enhance the photocatalytic efficiency. Compared to that of the recently representative MOFs, the k value of the photocatalytic reaction over Zr-BBI is as high as 0.073 min-1. With the consideration of the presented results, Zr-BBI can serve as a multifunctional platform for efficiently sensing and photoreducing Cr2O72- in an aqueous system, which fully illustrates the feasibility that introducing specific functional groups in the framework of MOFs would enhance the related photocatalytic activity.