Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution
Abstract Selective dechlorination of organic chlorides over hydrogen evolution reaction (HER) remains a challenge because of their coincidence. Nanoscale zerovalent iron (nFe0) draws a promising picture of in situ groundwater dechlorination, but its indiscriminate reactivity limits the application....
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2025-05-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202416663 |
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| author | Xiaohong Hu Qianhai Zhou Du Chen Zhongyuan Guo Yiman Gao Chaohuang Chen Jie Hou Vincent Noël Daohui Lin Lizhong Zhu Jiang Xu |
| author_facet | Xiaohong Hu Qianhai Zhou Du Chen Zhongyuan Guo Yiman Gao Chaohuang Chen Jie Hou Vincent Noël Daohui Lin Lizhong Zhu Jiang Xu |
| author_sort | Xiaohong Hu |
| collection | DOAJ |
| description | Abstract Selective dechlorination of organic chlorides over hydrogen evolution reaction (HER) remains a challenge because of their coincidence. Nanoscale zerovalent iron (nFe0) draws a promising picture of in situ groundwater dechlorination, but its indiscriminate reactivity limits the application. Here, nFe0 crystals are designed with electron shuttles and improved hydrophobic nature based on elemental chalcophile‐siderophile characteristics, where chalcophile‐siderophile S served as a bridge to allow impregnating nFe0 crystals with weakly siderophile and strongly chalcophile Cu. Even impregnations of lattice chalcophile‐siderophile elements into the nFe0 crystals are evidenced at both intraparticle and individual‐particle levels. The modulated Fe microenvironment and physicochemical properties broke the reactivity‐selectivity‐longevity‐stability trade‐off. Compared to nFe0, superhydrophobic Cu─S─nFe0 with lattice expansion promoted dechlorination by 20‐fold but inhibited HER by 150‐fold, utilizing ≈80–100% electrons from the Fe0 reservoir. This work demonstrates the concept of engineering nFe0 lattice with tunable structure‐property relationships, mimicking reductive dehalogenases by selectively interacting with halocarbon functional groups for efficient dehalogenation and sustainable groundwater remediation. |
| format | Article |
| id | doaj-art-649167f8bb774983a3f0225d81b04091 |
| institution | DOAJ |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-05-01 |
| publisher | Wiley |
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| series | Advanced Science |
| spelling | doaj-art-649167f8bb774983a3f0225d81b040912025-08-20T02:56:11ZengWileyAdvanced Science2198-38442025-05-011217n/an/a10.1002/advs.202416663Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen EvolutionXiaohong Hu0Qianhai Zhou1Du Chen2Zhongyuan Guo3Yiman Gao4Chaohuang Chen5Jie Hou6Vincent Noël7Daohui Lin8Lizhong Zhu9Jiang Xu10College of Environmental and Resource Sciences Zhejiang University Hangzhou 310058 ChinaCollege of Environmental and Resource Sciences Zhejiang University Hangzhou 310058 ChinaCollege of Environmental and Resource Sciences Zhejiang University Hangzhou 310058 ChinaCollege of Environmental and Resource Sciences Zhejiang University Hangzhou 310058 ChinaCollege of Environmental and Resource Sciences Zhejiang University Hangzhou 310058 ChinaCollege of Environmental and Resource Sciences Zhejiang University Hangzhou 310058 ChinaCollege of Environmental and Resource Sciences Zhejiang University Hangzhou 310058 ChinaStanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory Menlo Park CA 94025 USACollege of Environmental and Resource Sciences Zhejiang University Hangzhou 310058 ChinaCollege of Environmental and Resource Sciences Zhejiang University Hangzhou 310058 ChinaCollege of Environmental and Resource Sciences Zhejiang University Hangzhou 310058 ChinaAbstract Selective dechlorination of organic chlorides over hydrogen evolution reaction (HER) remains a challenge because of their coincidence. Nanoscale zerovalent iron (nFe0) draws a promising picture of in situ groundwater dechlorination, but its indiscriminate reactivity limits the application. Here, nFe0 crystals are designed with electron shuttles and improved hydrophobic nature based on elemental chalcophile‐siderophile characteristics, where chalcophile‐siderophile S served as a bridge to allow impregnating nFe0 crystals with weakly siderophile and strongly chalcophile Cu. Even impregnations of lattice chalcophile‐siderophile elements into the nFe0 crystals are evidenced at both intraparticle and individual‐particle levels. The modulated Fe microenvironment and physicochemical properties broke the reactivity‐selectivity‐longevity‐stability trade‐off. Compared to nFe0, superhydrophobic Cu─S─nFe0 with lattice expansion promoted dechlorination by 20‐fold but inhibited HER by 150‐fold, utilizing ≈80–100% electrons from the Fe0 reservoir. This work demonstrates the concept of engineering nFe0 lattice with tunable structure‐property relationships, mimicking reductive dehalogenases by selectively interacting with halocarbon functional groups for efficient dehalogenation and sustainable groundwater remediation.https://doi.org/10.1002/advs.202416663chalcophile‐siderophile elementsiron microenvironmentlattice engineeringselective dechlorination |
| spellingShingle | Xiaohong Hu Qianhai Zhou Du Chen Zhongyuan Guo Yiman Gao Chaohuang Chen Jie Hou Vincent Noël Daohui Lin Lizhong Zhu Jiang Xu Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution Advanced Science chalcophile‐siderophile elements iron microenvironment lattice engineering selective dechlorination |
| title | Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution |
| title_full | Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution |
| title_fullStr | Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution |
| title_full_unstemmed | Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution |
| title_short | Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution |
| title_sort | modulating iron crystals with lattice chalcophile siderophile elements for selective dechlorinations over hydrogen evolution |
| topic | chalcophile‐siderophile elements iron microenvironment lattice engineering selective dechlorination |
| url | https://doi.org/10.1002/advs.202416663 |
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