Electronic structure modulation of iron sites with fluorine coordination enables ultra-effective H2O2 activation
Abstract Electronic structure modulation of active sites is critical important in Fenton catalysis as it offers a promising strategy for boosting H2O2 activation. However, efficient generation of hydroxyl radicals (•OH) is often limited to the unoptimized coordination environment of active sites. He...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-03-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-46653-6 |
| _version_ | 1797259194391330816 |
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| author | Deyou Yu Licong Xu Kaixing Fu Xia Liu Shanli Wang Minghua Wu Wangyang Lu Chunyu Lv Jinming Luo |
| author_facet | Deyou Yu Licong Xu Kaixing Fu Xia Liu Shanli Wang Minghua Wu Wangyang Lu Chunyu Lv Jinming Luo |
| author_sort | Deyou Yu |
| collection | DOAJ |
| description | Abstract Electronic structure modulation of active sites is critical important in Fenton catalysis as it offers a promising strategy for boosting H2O2 activation. However, efficient generation of hydroxyl radicals (•OH) is often limited to the unoptimized coordination environment of active sites. Herein, we report the rational design and synthesis of iron oxyfluoride (FeOF), whose iron sites strongly coordinate with the most electronegative fluorine atoms in a characteristic moiety of F-(Fe(III)O3)-F, for effective H2O2 activation with potent •OH generation. Results demonstrate that the fluorine coordination plays a pivotal role in lowering the local electron density and optimizing the electronic structures of iron sites, thus facilitating the rate-limiting H2O2 adsorption and subsequent peroxyl bond cleavage reactions. Consequently, FeOF exhibits a significant and pH-adaptive •OH yield (~450 µM) with high selectivity, which is 1 ~ 3 orders of magnitude higher than the state-of-the-art iron-based catalysts, leading to excellent degradation activities against various organic pollutants at neutral condition. This work provides fundamental insights into the function of fluorine coordination in boosting Fenton catalysis at atomic level, which may inspire the design of efficient active sites for sustainable environmental remediation. |
| first_indexed | 2024-04-24T23:05:33Z |
| format | Article |
| id | doaj.art-1519dd8e7b2744c9af4b659c9c219998 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-04-24T23:05:33Z |
| publishDate | 2024-03-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-1519dd8e7b2744c9af4b659c9c2199982024-03-17T12:30:31ZengNature PortfolioNature Communications2041-17232024-03-0115111210.1038/s41467-024-46653-6Electronic structure modulation of iron sites with fluorine coordination enables ultra-effective H2O2 activationDeyou Yu0Licong Xu1Kaixing Fu2Xia Liu3Shanli Wang4Minghua Wu5Wangyang Lu6Chunyu Lv7Jinming Luo8Engineering Research Center for Eco-Dyeing and Finishing of Textiles (Ministry of Education), Zhejiang Sci-Tech UniversityEngineering Research Center for Eco-Dyeing and Finishing of Textiles (Ministry of Education), Zhejiang Sci-Tech UniversitySchool of Environmental Science and Engineering, Shanghai Jiao Tong UniversityCollege of Chemistry and Chemical Engineering, Qingdao UniversityEngineering Research Center for Eco-Dyeing and Finishing of Textiles (Ministry of Education), Zhejiang Sci-Tech UniversityEngineering Research Center for Eco-Dyeing and Finishing of Textiles (Ministry of Education), Zhejiang Sci-Tech UniversitySchool of Material Science & Engineering, Zhejiang Sci-Tech UniversitySchool of Environmental Science and Engineering, Shanghai Jiao Tong UniversitySchool of Environmental Science and Engineering, Shanghai Jiao Tong UniversityAbstract Electronic structure modulation of active sites is critical important in Fenton catalysis as it offers a promising strategy for boosting H2O2 activation. However, efficient generation of hydroxyl radicals (•OH) is often limited to the unoptimized coordination environment of active sites. Herein, we report the rational design and synthesis of iron oxyfluoride (FeOF), whose iron sites strongly coordinate with the most electronegative fluorine atoms in a characteristic moiety of F-(Fe(III)O3)-F, for effective H2O2 activation with potent •OH generation. Results demonstrate that the fluorine coordination plays a pivotal role in lowering the local electron density and optimizing the electronic structures of iron sites, thus facilitating the rate-limiting H2O2 adsorption and subsequent peroxyl bond cleavage reactions. Consequently, FeOF exhibits a significant and pH-adaptive •OH yield (~450 µM) with high selectivity, which is 1 ~ 3 orders of magnitude higher than the state-of-the-art iron-based catalysts, leading to excellent degradation activities against various organic pollutants at neutral condition. This work provides fundamental insights into the function of fluorine coordination in boosting Fenton catalysis at atomic level, which may inspire the design of efficient active sites for sustainable environmental remediation.https://doi.org/10.1038/s41467-024-46653-6 |
| spellingShingle | Deyou Yu Licong Xu Kaixing Fu Xia Liu Shanli Wang Minghua Wu Wangyang Lu Chunyu Lv Jinming Luo Electronic structure modulation of iron sites with fluorine coordination enables ultra-effective H2O2 activation Nature Communications |
| title | Electronic structure modulation of iron sites with fluorine coordination enables ultra-effective H2O2 activation |
| title_full | Electronic structure modulation of iron sites with fluorine coordination enables ultra-effective H2O2 activation |
| title_fullStr | Electronic structure modulation of iron sites with fluorine coordination enables ultra-effective H2O2 activation |
| title_full_unstemmed | Electronic structure modulation of iron sites with fluorine coordination enables ultra-effective H2O2 activation |
| title_short | Electronic structure modulation of iron sites with fluorine coordination enables ultra-effective H2O2 activation |
| title_sort | electronic structure modulation of iron sites with fluorine coordination enables ultra effective h2o2 activation |
| url | https://doi.org/10.1038/s41467-024-46653-6 |
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