Local control of S atoms on the Co-SACs for effective activation of PMS and degradation imidacloprid: Mechanism insights and toxicity evaluation
Imidacloprid (IMI), as an emerging pollutant, is frequently detected in pesticide wastewater. Cobalt-based single-atom catalysts (Co-SACs) doped with sulfur atoms can serve as an efficient strategy to activate peroxymonosulfate (PMS) and degrade organic pollutants. The paper employed density functio...
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Elsevier
2025-01-01
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| Series: | Ecotoxicology and Environmental Safety |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S0147651325000508 |
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| author | Zehua Wang JiaoXue Yang Guochun Lv Xiaomin Sun Hongjie Wang |
| author_facet | Zehua Wang JiaoXue Yang Guochun Lv Xiaomin Sun Hongjie Wang |
| author_sort | Zehua Wang |
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| description | Imidacloprid (IMI), as an emerging pollutant, is frequently detected in pesticide wastewater. Cobalt-based single-atom catalysts (Co-SACs) doped with sulfur atoms can serve as an efficient strategy to activate peroxymonosulfate (PMS) and degrade organic pollutants. The paper employed density functional theory and computational toxicology to deeply explore the mechanism and ecotoxicity of IMI when S atoms were introduced into Co-SACs for PMS activation. The result demonstrated that PMS can be preferentially decomposed into SO4•-, HO•, and 1O2 based on Co-S4-C0 active-center. It exhibited the most positive charge (+0.91 e-), highest electron transfer (0.84 e-), most negative adsorption energy (Eads = −53.85 kcal/mol), and longer O-O bond (1.48 Å). In the degradation processes of IMI, HO•-addition at the C2 sites and HO•-abstract at the H6 sites had the lowest Gibbs free barrier with 6.64 kcal/mol and 6.22 kcal/mol, respectively. Hydroxylation products were readily formed. Route 3 and 7 were the formation pathways of important experimental intermediates (PC3–4). Eco-toxicity assessment showed that most degradation products were completely harmless to aquatic toxicity. PC1–2, PC1–2, PC3–1, PC3–3, PC4–1 and PC4–2 showed similar and higher mutagenicity and bioaccumulation factors to the IMI. Therefore, Route 1, 3 and 4 contributed to the potential health risks. This study not only elucidated the atomic level relationship between PMS and Co-SACs, but also contributed to understanding the detailed degradation mechanism of IMI and the ecotoxicity of TPs. The finding provides theoretical support for environmental impacts of pesticide wastewater during advanced oxidation treatments. |
| format | Article |
| id | doaj-art-f6523b758d0549abb8c2f9581b606581 |
| institution | Kabale University |
| issn | 0147-6513 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Ecotoxicology and Environmental Safety |
| spelling | doaj-art-f6523b758d0549abb8c2f9581b6065812025-01-23T05:26:12ZengElsevierEcotoxicology and Environmental Safety0147-65132025-01-01289117714Local control of S atoms on the Co-SACs for effective activation of PMS and degradation imidacloprid: Mechanism insights and toxicity evaluationZehua Wang0JiaoXue Yang1Guochun Lv2Xiaomin Sun3Hongjie Wang4School of Eco-Environment, Hebei Key Laboratory of Close-to-Nature Restoration Technology of Wetlands, Hebei University, Baoding 071002, ChinaSchool of Geography and Environment, Liaocheng University, Liaocheng 252000, ChinaCollege of Environmental Sciences, Sichuan Agricultural University, Chengdu 611130, ChinaEnvironment Research Institute, Shandong University, Qingdao 266237, China; Corresponding authors.School of Eco-Environment, Hebei Key Laboratory of Close-to-Nature Restoration Technology of Wetlands, Hebei University, Baoding 071002, China; Corresponding authors.Imidacloprid (IMI), as an emerging pollutant, is frequently detected in pesticide wastewater. Cobalt-based single-atom catalysts (Co-SACs) doped with sulfur atoms can serve as an efficient strategy to activate peroxymonosulfate (PMS) and degrade organic pollutants. The paper employed density functional theory and computational toxicology to deeply explore the mechanism and ecotoxicity of IMI when S atoms were introduced into Co-SACs for PMS activation. The result demonstrated that PMS can be preferentially decomposed into SO4•-, HO•, and 1O2 based on Co-S4-C0 active-center. It exhibited the most positive charge (+0.91 e-), highest electron transfer (0.84 e-), most negative adsorption energy (Eads = −53.85 kcal/mol), and longer O-O bond (1.48 Å). In the degradation processes of IMI, HO•-addition at the C2 sites and HO•-abstract at the H6 sites had the lowest Gibbs free barrier with 6.64 kcal/mol and 6.22 kcal/mol, respectively. Hydroxylation products were readily formed. Route 3 and 7 were the formation pathways of important experimental intermediates (PC3–4). Eco-toxicity assessment showed that most degradation products were completely harmless to aquatic toxicity. PC1–2, PC1–2, PC3–1, PC3–3, PC4–1 and PC4–2 showed similar and higher mutagenicity and bioaccumulation factors to the IMI. Therefore, Route 1, 3 and 4 contributed to the potential health risks. This study not only elucidated the atomic level relationship between PMS and Co-SACs, but also contributed to understanding the detailed degradation mechanism of IMI and the ecotoxicity of TPs. The finding provides theoretical support for environmental impacts of pesticide wastewater during advanced oxidation treatments.http://www.sciencedirect.com/science/article/pii/S0147651325000508ImidaclopridDegradation mechanismSingle atom catalystsPeroxymonosulfate activationDensity functional theory |
| spellingShingle | Zehua Wang JiaoXue Yang Guochun Lv Xiaomin Sun Hongjie Wang Local control of S atoms on the Co-SACs for effective activation of PMS and degradation imidacloprid: Mechanism insights and toxicity evaluation Ecotoxicology and Environmental Safety Imidacloprid Degradation mechanism Single atom catalysts Peroxymonosulfate activation Density functional theory |
| title | Local control of S atoms on the Co-SACs for effective activation of PMS and degradation imidacloprid: Mechanism insights and toxicity evaluation |
| title_full | Local control of S atoms on the Co-SACs for effective activation of PMS and degradation imidacloprid: Mechanism insights and toxicity evaluation |
| title_fullStr | Local control of S atoms on the Co-SACs for effective activation of PMS and degradation imidacloprid: Mechanism insights and toxicity evaluation |
| title_full_unstemmed | Local control of S atoms on the Co-SACs for effective activation of PMS and degradation imidacloprid: Mechanism insights and toxicity evaluation |
| title_short | Local control of S atoms on the Co-SACs for effective activation of PMS and degradation imidacloprid: Mechanism insights and toxicity evaluation |
| title_sort | local control of s atoms on the co sacs for effective activation of pms and degradation imidacloprid mechanism insights and toxicity evaluation |
| topic | Imidacloprid Degradation mechanism Single atom catalysts Peroxymonosulfate activation Density functional theory |
| url | http://www.sciencedirect.com/science/article/pii/S0147651325000508 |
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