Ultrahigh charge utilization of C−C bridge-dependent MOF@COFs empowering sustainable removal of trace pharmaceuticals

Pharmaceutical contaminations pose serious threats to water quality and human health, while photocatalysis technology provides a solution to the decontamination. However, limited light energy transformation and severe charge recombination hamper the application of photocatalysts for broad-spectrum removal of trace pharmaceuticals. Here, the C − C bond as connection junction served to trigger the versatile synthesis of core-shell MOF@COFs with superior charge separation capability than corresponding parent COFs and MOFs, including MIL@V-TZ, MIL@DaV-TZ, and MIL@DaV-TAPB. The C − C bridge induced lower exciton binding energy (Eb, 42.66 meV) and overlap integral of electron-hole distribution (Sr, 0.57), endowing MIL@V-TZ with photocatalytic efficiencies of 9.8 − 70.2 min−1·g−1 for tetracycline, diclofenac, acetaminophen, and difloxacin. Based on the in-situ grown MIL@V-TZ film, a flow-through system was constructed to achieve ultra-efficient (>99%) and sustainable (up to 6000 min) pharmaceuticals removal without sacrificial agents. In-situ experiments revealed that the electrons were rapidly transferred and highly utilized to form •O2−, dominating the degradation of pharmaceuticals with reduced toxicity. By unveiling the role of C − C bridge in controllable assembly of heterostructures and boosting electron transfer, this work presents an avenue for water decontamination. Charge recombination hampers the effectiveness of photocatalysis in decontamination. A versatile strategy to design MOF@COFs enables the ultrahigh charge utilization for swift •O2− generation, accomplishing sustainable pharmaceuticals removal.