Modulating electron density enable efficient cascade conversion from peroxymonosulfate to superoxide radical driven by electron-rich/poor dual sites.

The superoxide radical (•O2-)-mediated peroxymonosulfate (PMS)-based photo-Fenton-like reaction enables highly selective water decontamination. Nevertheless, the targeted construction of •O2--mediated photo-Fenton-like system has been challenging. Herein, we developed an electron-rich/-poor dual sites driven •O2--mediated cascade photo-Fenton-like system by modulating electron density. Experimental and theoretical results demonstrated that PMS was preferentially adsorbed on electron-poor Co site. This adsorption promoted O-O bond cleavage of PMS to generate hydrogen peroxide (H2O2), which then migrated to electron-rich O site to extract eg electrons for O-H bond cleavage, rather than competing with PMS for Co site. The developed versatile cascade reaction system could selectively eliminate contaminants with low n-octanol/water partition constants (KOW) and dissociation constants (pKa) and remarkably resist inorganics (Cl-, H2PO4- and NO3-), humic acid (HA) and even real water matrices (tap water and secondary effluent). This finding provided a novel and plausible strategy to accurately and efficiently generate •O2- for the selective water decontamination.

Spin state-dependent in-situ photo-Fenton-like transformation from oxygen molecule towards singlet oxygen for selective water decontamination.

The development of 1O2-dominanted selective decontamination for water purification was hampered by extra H2O2 consumption and poor 1O2 generation. Herein, we proposed the reconstruction of Fe spin state using near-range N atom and long-range N vacancies to enable efficient generation of H2O2 and sequential activation of H2O2 into 1O2 after visible-light irradiation. Theoretical and experimental results revealed that medium-spin Fe(III) strengthened O2 adsorption, penetrated eg electrons to antibonding p-orbital of oxygen, and lowered the free energy of O2 activation, enabling the oxygen protonation for H2O2 generation. Thereafter, the electrons of H2O2 could be extracted by low-spin Fe(III) and rapidly converted into 1O2 in a nonradical path. The developed 1O2-dominated in-situ photo-Fenton-like system had an excellent pH universality and anti-interference to inorganic ions, dissolved organic matter, and even real water matrixes (e.g., tap water and secondary effluent). This work provided a novel insight for sustainable and efficient 1O2 generation, which motivated the development of new-generation selective water treatment technology.