Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution
HU Xiao-hong, Qianhai Zhou, Du Chen, Zhongyuan Guo, Yiman Gao, Chaohuang Chen, Jie Hou, Vincent Noël, Daohui Lin, Lizhong Zhu, Jiang Xu
Abstract
Abstract Selective dechlorination of organic chlorides over hydrogen evolution reaction (HER) remains a challenge because of their coincidence. Nanoscale zerovalent iron (nFe 0 ) draws a promising picture of in situ groundwater dechlorination, but its indiscriminate reactivity limits the application. Here, nFe 0 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 nFe 0 crystals with weakly siderophile and strongly chalcophile Cu. Even impregnations of lattice chalcophile‐siderophile elements into the nFe 0 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 nFe 0 , superhydrophobic Cu─S─nFe 0 with lattice expansion promoted dechlorination by 20‐fold but inhibited HER by 150‐fold, utilizing ≈80–100% electrons from the Fe 0 reservoir. This work demonstrates the concept of engineering nFe 0 lattice with tunable structure‐property relationships, mimicking reductive dehalogenases by selectively interacting with halocarbon functional groups for efficient dehalogenation and sustainable groundwater remediation.