Hydrogen Bonding in Amorphous Alkaline Earth Carbonates

Amorphous intermediates play a crucial role during the crystallization of alkaline earth carbonates. We synthesized amorphous carbonates of magnesium, calcium, strontium, and barium from methanolic solution. The local environment of water and the strength of hydrogen bonding in these hydrated modifications were probed with Fourier transform IR spectroscopy, H-1 NMR spectroscopy, and heteronuclear correlation experiments. Temperature-dependent spin-lattice (T1) relaxation experiments provided information about the water motion in the amorphous materials. The Pearson hardness of the respective divalent metal cation predominantly determines the strength of the internal hydrogen-bonding network. Amorphous magnesium carbonate deviates from the remaining carbonates, as it contains additional hydroxide ions, which act as strong hydrogen-bond acceptors. Amorphous calcium carbonate exhibits the weakest hydrogen bonds of all alkaline earth carbonates. Our study provides a coherent picture of the hydrogen bonding situation in these transient species and thereby contributes to a deeper understanding of the crystallization process of carbonates.