Theory-Guided Inelastic Neutron Scattering of Crystalline Alkaline Aluminate Salts Bearing Principal Motifs of Solution-State Species
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- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Washington State Univ., Pullman, WA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
Aluminate salts precipitated from caustic alkaline solutions exhibit a correlation between the anionic speciation and the identity of the alkali cation in the precipitate, with the aluminate ions occurring either in monomeric (Al(OH)4–) or dimeric (Al2O(OH)62–) forms. The origin of this correlation is poorly understood as are the roles that oligomeric aluminate species play in determining the solution structure, prenucleation clusters, and precipitation pathways. Characterization of aluminate solution speciation with vibrational spectroscopy results in spectra that are difficult to interpret because the ions access a diverse and dynamic configurational space. To investigate the Al(OH)4– and Al2O(OH)62– anions within a well-defined crystal lattice, inelastic neutron scattering (INS) and Raman spectroscopic data were collected and simulated by density functional theory for K2[Al2O(OH)6], Rb2[Al2O(OH)6], and Cs[Al(OH) 4]·2H2O. These structures capture archetypal solution aluminate species: the first two salts contain dimeric Al2O(OH)62– anions, while the third contains the monomeric Al(OH)4– anion. Here, comparisons were made to the INS and Raman spectra of sodium aluminate solutions frozen in a glassy state. In contrast to solution systems, the crystal lattice of the salts results in well-defined vibrations and associated resolved bands in the INS spectra. The use of a theory-guided analysis of the INS of this solid alkaline aluminate series revealed that differences were related to the nature of the hydrogen-bonding network and showed that INS is a sensitive probe of the degree of completeness and strength of the bond network in hydrogen-bonded materials. Results suggest that the ionic size may explain cation-specific differences in crystallization pathways in alkaline aluminate salts.
- Research Organization:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- 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; AC05-76RL01830; AC05-00OR22725
- OSTI ID:
- 1827595
- Report Number(s):
- LA-UR-21-28856
- Journal Information:
- Inorganic Chemistry, Vol. 60, Issue 21; ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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