Sulfur Loading and Speciation Control the Hydrophobicity, Electron Transfer, Reactivity, and Selectivity of Sulfidized Nanoscale Zerovalent Iron

Xu, Jiang; Avellan, Astrid; Li, Hao; Liu, Xitong; Noël, Vincent; Lou, Zimo; Wang, Yan; Kaegi, Rälf; Henkelman, Graeme; Lowry, Gregory V.

doi:10.1002/adma.201906910

Sulfur Loading and Speciation Control the Hydrophobicity, Electron Transfer, Reactivity, and Selectivity of Sulfidized Nanoscale Zerovalent Iron

Journal Article · Thu Mar 12 00:00:00 EDT 2020 · Advanced Materials

DOI:https://doi.org/10.1002/adma.201906910· OSTI ID:1633776

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Carnegie Mellon Univ., Pittsburgh, PA (United States)
Univ. of Texas, Austin, TX (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Univ. of Pittsburgh, PA (United States)
Swiss Federal Institute of Aquatic Science and Technology, Dübendorf (Switzerland)

Sulfidized nanoscale zerovalent iron (SNZVI) is a promising material for groundwater remediation. However, the relationships between sulfur content and speciation and the properties of SNZVI materials are unknown, preventing rational design. Here, the effects of sulfur on the crystalline structure, hydrophobicity, sulfur speciation, corrosion potential, and electron transfer resistance are determined. Sulfur incorporation extended the nano-Fe⁰ BCC lattice parameter, reduced the Fe local vacancies, and lowered the resistance to electron transfer. Impacts of the main sulfur species (FeS and FeS₂) on hydrophobicity (water contact angles) are consistent with density functional theory calculations for these FeS_x phases. These properties well explain the reactivity and selectivity of SNZVI during the reductive dechlorination of trichloroethylene (TCE), a hydrophobic groundwater contaminant. Controlling the amount and speciation of sulfur in the SNZVI made it highly reactive (up to 0.41 L m^-2 d^-1) and selective for TCE degradation over water (up to 240 moles TCE per mole H₂O), with an electron efficiency of up to 70%, and these values are 54-fold, 98-fold, and 160-fold higher than for NZVI, respectively. These findings can guide the rational design of robust SNZVI with properties tailored for specific application scenarios.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: NSF; National Institute of Health; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1633776

Alternate ID(s):: OSTI ID: 1604248

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 17 Vol. 32; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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