Silver-functionalized silica aerogel for iodine capture: Adsorbent aging by NO2 in spent nuclear fuel reprocessing off-gas

Shen, Ziheng; Wiechert, Alexander I.; Choi, Seungrag; Ladshaw, Austin P.; Tavlarides, Lawrence L.; Tsouris, Costas; Yiacoumi, Sotira

doi:10.1016/j.micromeso.2022.111898

Title: Silver-functionalized silica aerogel for iodine capture: Adsorbent aging by NO₂ in spent nuclear fuel reprocessing off-gas

Journal Article · 04 April 2022 · Microporous and Mesoporous Materials

DOI: https://doi.org/10.1016/j.micromeso.2022.111898 · OSTI ID:1872841

^[1]; Wiechert, Alexander I. ^[1]; Choi, Seungrag ^[2];

^[3]; Tavlarides, Lawrence L. ^[2];

^[4]; Yiacoumi, Sotira ^[1]

Georgia Institute of Technology, Atlanta, GA (United States)
Syracuse Univ., NY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Georgia Institute of Technology, Atlanta, GA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We report silver-functionalized silica aerogel (Ag⁰-Aerogel) is considered a promising porous adsorbent for the capture of iodine from nuclear fuel reprocessing off-gas. The Ag⁰-Aerogel, nevertheless, experiences a steady loss of capacity when exposed to NO₂ in the off-gas. This phenomenon is known as aging and its governing processes remain unclear. We exposed Ag⁰-Aerogel samples to 2% NO₂ in dry air at 150 °C for up to 1 month, followed by I₂ loading. Samples were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Our results elucidated the precise Ag species in Ag⁰-Aerogel that adsorb I₂: (i) Ag⁰ nanoparticles, (ii) Ag thiolates (Ag–S-r) covering the nanoparticles and the aerogel backbone, and (iii) Ag–S complexes including amorphous Ag₂S. We unraveled the two predominant underlying processes of aging in NO₂: (i) Ag–S-r is oxidized by NO₂ forming silver sulfonate (Ag–SO₃-r) which is oxidized further to silver sulfate (Ag₂SO₄) molecules, (ii) Ag₂SO₄ molecules then migrate from the pores to the aerogel surface and aggregate yielding Ag₂SO₄ particles that do not adsorb I₂. Plausible reaction pathways and aggregation mechanisms are explored. These findings may be used to guide the discovery of more advanced materials for iodine capture and the development of accurate predictive models.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC05-00OR22725; AC02-06CH11357

OSTI ID:: 1872841

Alternate ID(s):: OSTI ID: 1866435; OSTI ID: 1867478; OSTI ID: 1961446

Journal Information:: Microporous and Mesoporous Materials, Journal Name: Microporous and Mesoporous Materials Journal Issue: N/A Vol. 336; ISSN 1387-1811

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Silver-functionalized silica aerogel for iodine capture: Adsorbent aging by NO₂ in spent nuclear fuel reprocessing off-gas