Adsorption of water and formic acid molecules on the (104) surface of calcite: a theoretical study by DFT-D3

Abstract

Calcite is widely used in many fields. The synthesis of calcite is strongly influenced by solvents and additives. In this paper, the adsorption of water and formic acid molecules on the (104) surface of calcite was systematically studied on the atomic scale using the density functional theory (DFT) method. The results show that both molecules can be adsorbed on the calcite surface by occupying the top position of Ca. The results of differential charge density and the projected crystal orbital Hamiltonian population show that the adsorption is controlled by the charge transfer from the oxygen atom to the surface calcium. Formic acid has a carbonyl oxygen and it plays a greater role in stabilizing the surface than water. Moreover, the adsorption of two molecules can be further stabilized by hydrogen bonds formed between the hydrogen atom in the adsorbed molecules and the oxygen in calcite. This work provides a clear understanding of the stabilization of the calcite surface by adsorbing different molecules and also provides the possibility of tuning the synthesis of calcite by choosing a suitable solvent and additives.