Hourglass-shaped Europium Cluster-based Secondary Building Unit in Metal-organic Framework for Photocatalytic Wastewater Purification and Sterilization Via Enhanced Reactive Oxygen Species Production

A large number of diseases caused by water pollution have become a global public health issue, and the development and construction of innovative and efficient photocatalytic systems for water remediation is vital to improve water quality and prevent bacteria-induced diseases. Herein, a europium-based metal-organic framework (Eu-MOF) was self-assembled with complex hourglass-shaped Eu clusters as secondary building units (SBUs), achieving excellent photoinduced reactive oxygen species (ROS) generation ability. Moreover, Eu-MOF can quickly and efficiently degrade organic dyes and kill a variety of bacteria under low-power light irradiation conditions. Time-dependent scanning electron microscopy (SEM) and infrared absorption spectroscopy (IR) were used for the first time to track the formation process of complex clusters into cluster-based MOFs, and the gradual transformation of amorphous intermediates into crystalline Eu-MOF was clearly tracked. Electrochemical impedance spectroscopy (EIS) results showed that Eu-MOF has a smaller semicircle than the organic ligands, demonstrating its excellent charge separation ability. The excellent ROS generation capacity of Eu-MOF was jointly demonstrated by electron paramagnetic resonance (EPR) spectroscopy and the results obtained using the 2',7'-dichlorodihydrofluorescein (DCFH) indicator. More importantly, using low-power (60 mW/cm) Xe lamp irradiation, Eu-MOF can almost completely degrade 10 mg/L aqueous solutions of rhodamine B (RhB), methylene blue (MB), and crystal violet (CV) within 30, 90, and 120 min, respectively. In addition, the excellent light-induced ROS production ability of Eu-MOF contributes to its significant cell killing and antibacterial effects. Under light irradiation conditions, Eu-MOF can effectively kill Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), with average inhibition zone sizes of 2.54 ± 0.17 and 2.56 ± 0.08 cm, respectively. This work opens up new horizons for the build of efficient photocatalytic systems based on lanthanide porous materials and promotes the progress of lanthanide MOFs (Ln-MOFs) crystal engineering.