Inference of principal species in caustic aluminate solutions through solid-state spectroscopic characterization

Tetrahedrally coordinated aluminate Al(OH)₄^- and dialuminate Al₂O(OH)₆^2- anions are considered to be major species in aluminum-rich alkaline solutions. However, their relative abundance remains difficult to spectroscopically quantify due to local structure similarities and poorly understood effects arising from extent of polymerization and counter-cations. To help unravel these relationships here we report detailed characterization of three solid-phase analogues as structurally and compositionally well-defined reference materials. We successfully synthesized a cesium salt of the aluminate monomer, CsAl(OH)₄·2H₂O, for comparison to potassium and rubidium salts of the aluminate dimer, K₂Al₂O(OH)₆, and Rb₂Al₂O(OH)₆, respectively. Single crystal and powder X-ray diffraction methods clearly reveal the structure and purity of these materials for which a combination of ²⁷Al MAS-NMR, Al K-edge X-ray absorption and Raman/IR spectroscopies was then used to fingerprint the two major tetrahedrally coordinated Al species. The resulting insights into the effect of Al-O-Al bridge formation between aluminate tetrahedra on spectroscopic features may also be generalized to the many materials that are based on this motif.