Spin state-tailored tetrahedral and octahedral cobalt centers on millimetric Co-Al oxide catalysts as dual sites for synergistic peroxymonosulfate activation

• Published in: Applied catalysis. B, Environmental Vol. 342; p. 123466
• Main Authors: Yang, Jia-Cheng E., Zhu, Min-Ping, Guan, Daqin, Yuan, Baoling, Sun, Darren Delai, Sun, Chenghua, Fu, Ming-Lai
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.03.2024
• Subjects: Electron spin state; Millimetric Co-Al oxide; Peroxymonosulfate; γ-Al2O3; Millimetric Co-Al oxide; Peroxymonosulfate; Electron spin state; γ-Al2O3
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2023.123466

Rationally developing millimetric metal catalysts with tailored electron function is crucial for water decontamination, but challenges remain due to insufficient understanding on their electronic structure engineering and the underlying mechanism. Here, through constructing bonded Co-O-Al unit sites on the millimetric γ-Al2O3 spheres, we report a feasible and scalable strategy of modulating the 3d electron configurations and spin states of supported tetrahedral and octahedral cobalt cations just by adjusting the radius of support curvature. The tetrahedral and octahedral cobalt centers with tailored electron spin states showed a synergism in peroxymonosulfate activation to generate SO4• and reactive oxygen (O*), in which the latter was converted into 1O2 and O2•. The electronic structure-oriented spin catalysis affected the formation of reactive species and the pathway of pollutant degradation. This work will stimulate the design and mass production of macroscopic spin catalysts with superior activity, reusability and stability for catalytic water purification. [Display omitted] •Tetrahedral and octahedral cobalt centers on macroscopic Co oxides were designed.•The spin states of Co centers dispersed on the macroscopic catalysts were tailored.•Spin state-related catalytic activity in peroxymonosulfate activation were reported.•Tetrahedral and octahedral Co sites showed a synergism of producing reactive species.