Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution

Hu, Xiaohong [Zhejiang Univ., Hangzhou (China)] (ORCID:0000000344909921); Zhou, Qianhai [Zhejiang Univ., Hangzhou (China)]; Chen, Du [Zhejiang Univ., Hangzhou (China)]; Guo, Zhongyuan [Zhejiang Univ., Hangzhou (China)]; Gao, Yiman [Zhejiang Univ., Hangzhou (China)]; Chen, Chaohuang [Zhejiang Univ., Hangzhou (China)]; Hou, Jie [Zhejiang Univ., Hangzhou (China)]; Noël, Vincent [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)]; Lin, Daohui [Zhejiang Univ., Hangzhou (China)]; Zhu, Lizhong [Zhejiang Univ., Hangzhou (China)]; Xu, Jiang [Zhejiang Univ., Hangzhou (China)] (ORCID:0000000303694848)

doi:10.1002/advs.202416663

DOE OSTI · 2575026

Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution

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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.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY chalcophile-siderophile elements iron microenvironment lattice engineering selective dechlorination

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Hu, Xiaohong [Zhejiang Univ., Hangzhou (China)] (ORCID:0000000344909921), Zhou, Qianhai [Zhejiang Univ., Hangzhou (China)], Chen, Du [Zhejiang Univ., Hangzhou (China)], Guo, Zhongyuan [Zhejiang Univ., Hangzhou (China)], Gao, Yiman [Zhejiang Univ., Hangzhou (China)], Chen, Chaohuang [Zhejiang Univ., Hangzhou (China)], Hou, Jie [Zhejiang Univ., Hangzhou (China)], Noël, Vincent [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)], Lin, Daohui [Zhejiang Univ., Hangzhou (China)], Zhu, Lizhong [Zhejiang Univ., Hangzhou (China)], Xu, Jiang [Zhejiang Univ., Hangzhou (China)] (ORCID:0000000303694848). 2025-03-07. Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution. https://doi.org/10.1002/advs.202416663

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