Radiolytic Production of Radical Species in Gibbsite Doped with Iron and Chromium Ions

Hlushko, Hanna; Ramos-Ballesteros, Alejandro; Bedar, Amita; Chen, Ping; Zhang, Xin; Colina Ruiz, Roberto A.; Rosso, Kevin M.; Pearce, Carolyn I.; LaVerne, Jay A.

doi:10.1021/acs.jpcc.5c05004

Title: Radiolytic Production of Radical Species in Gibbsite Doped with Iron and Chromium Ions

Journal Article · Sun Sep 07 00:00:00 UTC 2025 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.5c05004 · OSTI ID:3028499

^[1]; Ramos-Ballesteros, Alejandro ^[1]; Bedar, Amita ^[2]; Chen, Ping ^[3];

^[3]; Colina Ruiz, Roberto A. ^[3];

^[3];

^[2]

University of Notre Dame, IN (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)
University of Notre Dame, IN (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Gibbsite (aluminum hydroxide, Al(OH)₃) nanoparticles, synthesized from aluminum chloride or aluminum nitrate, were doped with metal ions, Cr(III) or Fe(III), and then irradiated with γ rays to determine the effect of the dopants on radiolytic hydrogen (H₂) production and radical generation. The addition of Cr(III) and Fe(III) ions at concentrations of 0.5% or 5% decreased the concentration of stable oxygen-centered radicals, with the strongest suppression in Cr(III) doped samples. A decrease in H₂ yields was observed with increasing Cr(III) or Fe(III) concentrations, with the greatest effect observed for the Fe(III)-doped samples. Reduction of the Cr(III) to Cr(II) and Fe(III) to Fe(II) was also observed, probably due to scavenging of radiolytically produced electrons. However, further processes differ for Fe(III)- and Cr(III)-doped systems. Both ions are reduced by the free electrons, leading to a decrease in H₂ production, but they react differently with the oxygen radicals. Cr(III) can be oxidized by oxygen radicals, whereas Fe(III) cannot. Fe(II) can interact with peroxides, possible products of intermediate oxygen oxidation, converting back to Fe(III) and leaving oxygen radicals behind. These oxidation reactions lead to a difference in the observed relative effects on H₂ yields and oxygen radical production between Cr(III)- and Fe(III)-doped gibbsite. In conclusion, the connection between electron scavenging and H₂ production indicates that radiolytically produced electrons are precursors to H₂.

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Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; AC07-05ID14517; FC02-04ER15533

OSTI ID:: 3028499

Report Number(s):: INL/JOU-25-87292; PNNL-SA-213157

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 37 Vol. 129; ISSN 1932-7455; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Radiolytic Production of Radical Species in Gibbsite Doped with Iron and Chromium Ions

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References (49)

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