Bioinspired axial S-coordinated single-atom cobalt catalyst to efficient activate peroxymonosulfate for selective high-valent Co-Oxo species generation

化学 催化作用 电子转移 光化学 无机化学 有机化学
作者
Chunyao Gu,Yaqin Zhang,Peng He,Min Gan,Jianyu Zhu,Huaqun Yin
出处
期刊:Journal of Hazardous Materials [Elsevier BV]
卷期号:472: 134515-134515 被引量:17
标识
DOI:10.1016/j.jhazmat.2024.134515
摘要

The efficient activation and selective high-valent metal-oxo (HVMO) species generation remain challenging for peroxymonosulfate (PMS)-based advanced oxidation processes (PMS-AOPs) in water purification. The underlying mechanism of the activation pathway is ambiguous, leading to a massive dilemma in the control and regulation of HVMO species generation. Herein, bioinspired by the bio-oxidase structure of cytochrome P450, the axial coordination strategy was adopted to tailor a single-atom cobalt catalyst (CoN4S-CB) with an axial S coordination. CoN4S-CB high-selectively generated high-valent Co-Oxo species (Co(IV)=O) via PMS activation. Co(IV)=O demonstrated an ingenious oxygen atom transfer (OAT) reaction to achieve the efficient degradation of sulfamethoxazole (SMX), and this allowed robust operation in various complex environments. The axial S coordination modulated the 3d orbital electron distribution of the Co atom. Density functional theory (DFT) calculation revealed that the axial S coordination decreased the energy barrier for PMS desorption and lowered the free energy change (ΔG) for Co(IV)=O generation. CoN4S-PMS* had a narrow d-band close to the Fermi level, which enhanced charge transfer to accelerate the cleavage of O-O and O-H bonds in PMS. This work provides a broader perspective on the activator design with natural enzyme structure-like active sites to efficient activate PMS for selective HVMO species generation. The design of activators with natural structures offers a valid approach for peroxymonosulfate (PMS) activation. Bioinspired by cytochrome P450, the axial coordination strategy tailored a single-atom cobalt catalyst (CoN4S-CB) with an axial S coordination. CoN4S-CB effectively activated PMS and selectively generated high-valent Co-Oxo species (Co(IV)=O), which degraded sulfamethoxazole via oxygen atom transfer reaction. The axial S coordination modulated the electron distribution of the Co 3d orbital, which favored O-O and O-H cleavage in PMS and Co(VI)=O generation. The mechanism that controls the activation pathway is clarified, facilitating the future development of bioinspired catalysts for PMS activation and HVMO-mediated water purification.
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