skip to main content

Title: Electrochemical and spectroscopic evidence on the one-electron reduction of U(VI) to U(V) on magnetite

Reduction of U(VI) to U(IV) on mineral surfaces has been considered as a one-step two electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies indicates U(VI) can undergo a one electron reduction to U(V) without further progression to U(IV). We investigated the mechanisms of uranium reduction by reducing U(VI) electrochemically on a magnetite electrode at pH 3.4 . The one electron reduction of U(VI) was first confirmed using the cyclic voltammetry method. Formation of nano-size uranium precipitates on the surface of magnetite at reducing potentials and dissolution of the solids at oxidizing potentials were observed by in situ electrochemical AFM. XPS analysis of the magnetite electrodes polarized in uranium solutions at voltages from 0.1 ~ 0.9 V (vs. Ag/AgCl) showed the presence of only U(V) and U(VI). The highest amount of U(V) relative to U(VI) was prepared at 0.7 V, where the longest average U–Oaxial distance of 2.05 ± 0.01 Å was evident in the same sample revealed by EXAFS analysis. The results demonstrate that the electrochemical reduction of U(VI) on magnetite only yields U(V), even at a potential of 0.9 V, which favors the one-electron reduction mechanism. U(V) did not disproportionate but stabilized onmore » magnetite through precipitation of mixed-valence state U(VI)/U(V) solids.« less
 [1] ;  [2] ;  [3] ;  [1] ;  [1] ;  [1]
  1. Univ. of Michigan, Ann Arbor, MI (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 0013-936X; KC0302060
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Environmental Science and Technology; Journal Volume: 49; Journal Issue: 10
American Chemical Society (ACS)
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org:
Country of Publication:
United States
uranium; magnetite; reduction; electrochemstry