Selective dechlorination of organic chlorides over hydrogen evolution reaction (HER) remains a challenge because of their coincidence. Nanoscale zerovalent iron (nFe) draws a promising picture of in situ groundwater dechlorination, but its indiscriminate reactivity limits the application. Here, nFe 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 crystals with weakly siderophile and strongly chalcophile Cu. Even impregnations of lattice chalcophile-siderophile elements into the nFe 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, superhydrophobic Cu─S─nFe with lattice expansion promoted dechlorination by 20-fold but inhibited HER by 150-fold, utilizing ≈80-100% electrons from the Fe reservoir. This work demonstrates the concept of engineering nFe lattice with tunable structure-property relationships, mimicking reductive dehalogenases by selectively interacting with halocarbon functional groups for efficient dehalogenation and sustainable groundwater remediation.
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