Unraveling Gibbsite Transformation Pathways into LiAl-LDH in Concentrated Lithium Hydroxide

Graham, Trenton R.; Hu, Jian Z.; Zhang, Xin; Dembowski, Mateusz; Jaegers, Nicholas R.; Wan, Chuan; Bowden, Mark E.; Lipton, Andrew S.; Felmy, Andrew R.; Clark, Sue B.; Rosso, Kevin M.; Pearce, Carolyn I.

doi:10.1021/acs.inorgchem.9b02000

Title: Unraveling Gibbsite Transformation Pathways into LiAl-LDH in Concentrated Lithium Hydroxide

Journal Article · Mon Sep 16 00:00:00 EDT 2019 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.9b02000· OSTI ID:1576778

^[1];

^[1]; Zhang, Xin ^[1];

^[1]; Jaegers, Nicholas R. ^[1]; Wan, Chuan ^[2]; Bowden, Mark E. ^[1];

^[1]; Felmy, Andrew R. ^[1]; Clark, Sue B. ^[1];

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

BATTELLE (PACIFIC NW LAB)
UNIVERSITY PROGRAMS

The intercalation of lithium (Li+) ions into metallic hydroxides (e.g. gibbsite, Al(OH)3) facilitates the synthesis of layered double hydroxides. Caustic environments, such as in lithium hydroxide (LiOH) solutions, present additional pathways beyond the intercalation of ions, specifically dissolution/precipitation processes. Herein, the phase transformation Al(OH)3 to lithium aluminum hydroxide dihydrate, Li[Al(OH)3)]2OH•2H2O in partially deuterated LiOH solutions is tracked through multinuclear, magic angle spinning, high-field nuclear magnetic resonance spectroscopy (27Al and 6Li MAS-NMR) , X-ray diffraction, and scanning electron microscopy of harvested solids. At high magnetic fields (19.975 T), 27Al MAS-NMR enabled detection and quantification of the reactive interface between Al(OH)3 and Li[Al(OH)3)]2OH•2H2O. 6Li MAS-NMR spectra collected on the harvested solids exhibited exchange mediated narrowing as the reaction time progressed, consistent with transport of Li+ ions between the interface and the bulk Li[Al(OH)3)]2OH•2H2O. Complimentary in-situ 27Al MAS-NMR at lower magnetic fields (7.046 T) utilized unique rotors capable of simultaneous resolution of solution and solid state Al-species in caustic environments. The reaction between Al(OH)3 (0.5 M) and LiOH (3 M) initially exhibited greater dissolution and formation of Al(OH)4- than the precipitation. Over several hours, the supersaturated Al(OH)4- solution precipitated Li[Al(OH)3)]2OH•2H2O. Simultaneous, in-situ observations of the solid component tracked the formation of Li[Al(OH)3)]2OH•2H2O evident by an increase in signal and narrowing of the Oh resonance. These results provides insight into Al precipitation in alkaline media with applications ranging from the reduction of Al content in Hanford site, high-level radioactive waste (HLRW) to the precipitation of LDH materials for application as catalyst materials, drug delivery devices, and ion-ion exchangers.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1576778

Report Number(s):: PNNL-SA-138626

Journal Information:: Inorganic Chemistry, Vol. 58, Issue 18

Country of Publication:: United States

Language:: English

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