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Cover art caption: The formation of environmentally persistent free radicals in metal–organic frameworks derivatives and the roles of environmentally persistent free radicals in photocatalysis.
•·EPFRs have been detected in several MOFs derivatives.•·The formation process of EPFRs in Bi-MOLs derivatives was simply proposed.•·The catalytic performance was correlated with the concentration of EPFRs.•·The EPFRs promoted the generation of ROS radicals through three reaction pathways.
Formation of environmentally persistent free radicals (EPFRs) on carbonaceous material has aroused increasing research attentions. In terms of metal organic frameworks (MOFs) derivatives, however, scarce studies have dedicated to the relevant aspects. Herein, EPFRs have been detected in Bi-metal organic layers (Bi-MOLs) derivatives. The corresponding g-factors and concentrations of EPFRs on Bi2O3@C by pyrolyzed at different temperatures were 2.0041–2.0046 and 7.04 × 1019-1.77 × 1020 spins/g, respectively. Interestingly, similar EPFRs signals were also monitored in HKUST-1 based and UiO-66 based derivatives. We observed that Bi2O3@C system with the highest EPFRs concentration exhibited superior degradation and mineralization efficiency for phenol and tetracycline. Its excellent photocatalytic performance was mainly attributed to the interaction between the internal EPFRs and photoinduced active species, which promoted more generation of reactive oxygen species (ROS) radicals. This hypothesis was supported by line correlations for EPFRs concentration vs. degradation kinetics in samples pyrolyzed at different temperatures (R2 = 0.946). Most significantly, mechanism investigation combined with DFT calculation indicated that the EPFRs not only promote the generation of 1O2 and •OH via molecular oxygen activation pathway but also provided a possibility of enhancing water oxidation by holes. These findings pave the way for MOFs derivative's implication and insight into the role of EPFRs in photocatalysis.