Enhanced Fluoride Uptake by Layered Double Hydroxides under Alkaline Conditions: Solid-State NMR Evidence of the Role of Surface >MgOH Sites

Layered double hydroxides (LDHs) are potential low-cost filter materials for use in fluoride removal from drinking water, but molecular-scale defluoridation mechanisms are lacking. In this research, we employed 19F solid-state NMR spectroscopy to identify fluoride sorption products on 2:1 MgAl LDH and to reveal the relationship between fluoride sorption and the LDH structure. A set of six 19F NMR peaks centered at −140, −148, −156, −163, −176, and −183 ppm was resolved. Combining quantum chemical calculations based on density function theory (DFT) and 19F­{27Al} transfer of populations in double resonance (TRAPDOR) analysis, we could assign the peaks at −140, −148, −156, and −163 ppm to Al–F (F coordinated to surface Al) and those at −176 and −183 ppm to Mg–F (F coordinated to surface Mg only). Interestingly, the spectroscopic data reveal that the formation of Al–F is the predominant mode of F– sorption at low pH, whereas the formation of Mg–F is predominant at high pH (or a higher Mg/Al ratio). This finding supports the fact that the F– uptake of 2:1 MgAl LDH was nearly six times that of activated alumina at pH 9. Overall, we explicitly revealed the different roles of the surface >MgOH and >AlOH sites of LDHs in defluoridation, which explained why the use of classic activated alumina for defluoridation is limited at high pH. The findings from this research may also provide new insights into material screening for potential filters for F– removal under alkaline conditions.