Superoxide radicals mediated by high-spin Fe catalysis for organic wastewater treatment.

Water resources are indispensable basic resources and important environmental carriers; the presence of organic contaminants in wastewater poses considerable risks to the health of both humans and ecosystems. Although the Fenton-like reactions using H2O2 as the oxidant to destroy organic pollutants are attractive, there are still challenges in improving reaction activity under neutral or even alkaline conditions. Herein, we designed a H2O2 activation pathway with O2•- as the main active species and elucidated that the spin interaction between Fe sites and coordinated O atoms effectively promotes the generation of the key intermediate Fe-*OOH. Furthermore, we successfully captured and analyzed the Fe-*OOH intermediate by in situ Raman spectroscopy. When applying FBOB to a continuous-flow reactor, CIP removal efficiency remained at around 90% within 600 min of continuous operation, achieving excellent efficiency, stability, and pH tolerance in removing pollutants.

Dynamic active-site induced by host-guest interactions boost the Fenton-like reaction for organic wastewater treatment.

In heterogeneous catalysis, uncovering the dynamic evolution of active sites in the working conditions is crucial to realizing increased activity and enhanced stability of catalyst in Fenton-like activation. Herein, we capture the dynamic changes in the unit cell of Co/La-SrTiO3 catalyst during the exemplary peroxymonosulfate activation process using X-ray absorption spectroscopy and in situ Raman spectroscopy, revealing the substrate tuned its structural evolution, which is the reversible stretching vibration of O-Sr-O and Co/Ti-O bonds in different orientations. This process effectively promotes the generation of key SO5* intermediates, which is beneficial to the formation of 1O2 and SO4•- from persulfate on the Co active site. Density functional theory and X-ray absorption spectroscopy show that the optimized structural distortion enhanced the metal-oxygen bond strength by tuning the eg orbitals and increased the number of transferred electrons to peroxymonosulfate by about 3-fold, achieving excellent efficiency and stability in removing organic pollutants.

Regulating Spin Polarization through Cationic Vacancy Defects in Bi4 Ti3 O12 for Enhanced Molecular Oxygen Activation.

Molecular oxygen (O2 ) activation technology is of great significance in environmental purification due to its eco-friendly operation and cost-effective nature. However, the activation of O2 is limited by spin-forbidden transitions, and efficient molecular oxygen activation depends on electronic behavior and surface adsorption. Herein, we prepared cationic defect-rich Bi4 Ti3 O12 (BTO-MV2) catalysts containing Ti vacancies (VTi ) for O2 activation in water purification. The VTi on BTO nanosheets can induce electron spin polarization, increasing the number of spin-down photogenerated electrons and reducing the recombination of electron-hole pairs. An active surface VTi is also formed, serving as a center for adsorbing O2 and extracting electrons, effectively generating ⋅OH, O2 ⋅- and 1 O2 . The degradation rate constant of tetracycline achieved by BTO-MV2 is 3.3 times faster than BTO, indicating a satisfactory prospect for practical application. This work provides an efficient pathway to activate molecular oxygen by constructing new active sites through cationic vacancy modification technology.