Structure and reactivity of sodium aluminate complexes in alkaline solutions

Nienhuis, Emily T.; Pouvreau, Maxime; Graham, Trent R.; Prange, Micah P.; Page, Katharine; Loring, John S.; Stack, Andrew G.; Clark, Aurora E.; Schenter, Gregory K.; Rosso, Kevin M.; Pearce, Carolyn I.; Wang, Hsiu-Wen

doi:10.1016/j.molliq.2022.120379

Structure and reactivity of sodium aluminate complexes in alkaline solutions

Journal Article · Fri Sep 16 00:00:00 EDT 2022 · Journal of Molecular Liquids

DOI:https://doi.org/10.1016/j.molliq.2022.120379· OSTI ID:1897826

^[1]; Pouvreau, Maxime ^[2]; Graham, Trent R. ^[1]; Prange, Micah P. ^[1]; ^[3]; Loring, John S. ^[1]; ^[4]; ^[5]; ^[1]; Rosso, Kevin M. ^[1]; Pearce, Carolyn I. ^[2]; ^[4]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Washington State Univ., Pullman, WA (United States)

The underlying mechanism by which tetrahedrally-coordinated aluminate solution species react to precipitate octahedrally-coordinated Al³⁺ in gibbsite is unknown. Sodium aluminate solutions provide the opportunity to investigate the role of ion speciation and local structure in the reaction, as the solution metastability can be controlled by varying ratio of excess NaOD to Al³⁺. Here, in this paper, capitalizing on this tunable precipitation behavior, aluminate speciation was investigated through a combination of Raman, infrared, and NMR spectroscopies, together with geometrical fitting of neutron and X-ray radial distribution functions. These techniques reveal a mixture of monomeric Al(OD)₄– and dimeric Al₂O(OD)₆^2- in all compositions, but solutions avoiding precipitation for extended timescales (i.e. months to years) show an increased dimeric Al₂O(OD)₆^2- population formed at the expense of the Al(OD)₄– monomer. Conversion between these species, as well the potential for further oligomerization and formation of larger pre-nucleation species is driven by the hydrogen/deuterium bonding (H/D-bonding) and proton/deuteron transfer reactions. Changes within the local environment around the aluminate anions, including solvation and the presence of solvent-shared ion pairs or contact ion pairs, will consequently govern the reactivity of these aluminate species to either promote or inhibit precipitation.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; AC05-76RL01830

OSTI ID:: 1897826

Alternate ID(s):: OSTI ID: 1901299
OSTI ID: 1902396
OSTI ID: 1971350

Report Number(s):: PNNL-SA-175319

Journal Information:: Journal of Molecular Liquids, Journal Name: Journal of Molecular Liquids Journal Issue: A Vol. 367; ISSN 0167-7322

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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