Affiliation:
1. Shenzhen Key Laboratory of Ecological Remediation and Carbon Sequestration, Guangdong Provincial Engineering Research Center for Urban Water Recycling and Environmental Safety, Institute of Environment and Ecology, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, People’s Republic of China
Abstract
The high-valent cobalt–oxo species (Co(IV)=O) is being increasingly investigated for water purification because of its high redox potential, long half-life, and antiinterference properties. However, generation of Co(IV)=O is inefficient and unsustainable. Here, a cobalt-single-atom catalyst with N/O dual coordination was synthesized by O-doping engineering. The O-doped catalyst (Co-OCN) greatly activated peroxymonosulfate (PMS) and achieved a pollutant degradation kinetic constant of 73.12 min
−1
g
−2
, which was 4.9 times higher than that of Co-CN (catalyst without O-doping) and higher than those of most reported single-atom catalytic PMS systems. Co-OCN/PMS realized Co(IV)=O dominant oxidation of pollutants by increasing the steady-state concentration of Co(IV)=O (1.03 × 10
−10
M) by 5.9 times compared with Co-CN/PMS. A competitive kinetics calculation showed that the oxidation contribution of Co(IV)=O to micropollutant degradation was 97.5% during the Co-OCN/PMS process. Density functional theory calculations showed that O-doping influenced the charge density (increased the Bader charge transfer from 0.68 to 0.85 e), optimized the electron distribution of the Co center (increased the d-band center from −1.14 to −1.06 eV), enhanced the PMS adsorption energy from −2.46 to −3.03 eV, and lowered the energy barrier for generation of the key reaction intermediate (*O*H
2
O) during Co(IV)=O formation from 1.12 to 0.98 eV. The Co-OCN catalyst was fabricated on carbon felt for a flow-through device, which achieved continuous and efficient removal of micropollutants (degradation efficiency of >85% after 36 h operation). This study provides a new protocol for PMS activation and pollutant elimination through single-atom catalyst heteroatom-doping and high-valent metal–oxo formation during water purification.
Funder
National Natural Science Foundation of China
Science, Technology and Innovation Commission of Shenzhen Municipality
Publisher
Proceedings of the National Academy of Sciences
Cited by
96 articles.
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