Influence of soluble oligomeric aluminum on precipitation in the Al–KOH–H2O system

Dembowski, Mateusz; Graham, Trent R.; Reynolds, Jacob G.; Clark, Sue B.; Rosso, Kevin M.; Pearce, Carolyn I.

doi:10.1039/d0cp04820h

Title: Influence of soluble oligomeric aluminum on precipitation in the Al–KOH–H₂O system

Journal Article · Mon Oct 26 00:00:00 EDT 2020 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d0cp04820h· OSTI ID:1756823

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^[1]; Pearce, Carolyn I. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Washington River Protection Solutions, Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

The role of oligomeric aluminate species in the precipitation of aluminum (Al) phases such as gibbsite (α-Al(OH)₃) from aqueous hydroxide solutions remains unclear and difficult to probe directly, despite its importance for developing accurate predictions of Al solubility in highly alkaline systems. Precipitation in this system entails a transition from predominantly tetrahedrally coordinated aluminate (Al(OH)₄^–) species in solution to octahedrally coordinated Al in gibbsite. In this paper, we report a quantitative study of dissolved Al in the Al–KOH–H₂O system using a combination of molecular spectroscopies. We establish a relationship between changes in ²⁷Al NMR chemical shifts and the relative intensity of Raman vibrational bands, indicative of variations in the ensemble speciation of Al in solution, and the formation of unique contact ion pair interactions with the aluminate dimer, Al₂O(OH)₆^2–. A strong correlation between the extent of Al oligomerization and the amount of solvated Al was demonstrated by systematically varying the KOH : Al molar ratio. The concentration of dissolved oligomeric Al in solution also directly impacted the particle size and morphology of the precipitated gibbsite. High concentrations of dimeric Al₂O(OH)₆^2– yielded smaller and more numerous anhedral to subhedral gibbsite particles, while low concentrations yielded fewer and larger euhedral gibbsite platelets. The collective observations suggest a key role for the Al₂O(OH)₆^2– dimer in promoting gibbsite precipitation from solution, with the potassium ion-paired dimer catalyzing a more rapid transformation of Al from tetrahedral coordination in solution to octahedral coordination in gibbsite.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: 89233218CNA000001; 436923.9; 49771; AC05-76RL01830

OSTI ID:: 1756823

Alternate ID(s):: OSTI ID: 1686234

Report Number(s):: LA-UR-20-22916

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 22, Issue 42; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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