Mechanochemical synthesis of low-fluorine doped aluminum hydroxide fluorides

Different aluminum hydroxide fluorides with varying Al/F molar ratios from 1:1.5 up to 1:0.05 were successfully synthesized by mechanochemical reactions. The characterization of the products by XRD, ²⁷Al and ¹⁹F MAS NMR, thermal analysis, nitrogen adsorption and zeta potential techniques allows a detailed understanding of the structure and surface properties of the products. Using γ-Al(OH)₃ and β-AlF₃·3H₂O as OH- and F-sources, respectively, strongly disordered products were obtained with an Al: F molar ratio higher than 1:0.25. The fluorination degree has affected the amount of 4- and 5-fold coordinated Al sites, not present in the reactants. An evolution of the sub-coordinated Al-species has been detected also as a consequence of annealing processes. Obviously, these species affect the phase transition to alumina, by decreasing the transition temperature of the formation of α-Al₂O₃. Synthesis conditions (milling time, fluorination degree) play a crucial role for the product composition. - Graphical abstract: The impact of the combined action of the milling and the different fluorine doping on the structure of new aluminum hydroxide fluorides was followed by ²⁷Al and ¹⁹F NMR and by other complementary techniques. - Highlights: • Low F-doped Al-hydroxide fluorides can be successfully prepared by mechanosynthesis. • Both F-doping and mechanochemical synthesis introduce a high number of defects in the structure. • The fluorination degree affects the amount of 4- and 5-fold coordinated Al sites as well as the transition temperature to corundum.