Unravelling phosphate adsorption on hydrous ferric oxide surfaces at the molecular level

The thorough understanding of the adsorption mechanism of phosphate on hydrous ferric oxides is necessary to deal with the environmental issues related to high phosphate concentrations in soils and open water. In this work, we consider three different adsorption geometries (monodentate and bidentate chemisorption and physisorption) and calculate the adsorption geometries and related adsorption energies at optPBE-vdW level. Using the Maxwell-Boltzmann distribution, it is estimated that about 83% of the phosphate molecules is in a monodentate chemisorption configuration, while 17% is physisorbed. Furthermore, theoretical infra-red spectra are obtained and compared to equivalent experimental spectra, supporting the conclusion that mainly monodentate chemisorption and physisorption occur. Most interestingly, a weighed infra-red spectrum is then calculated, using the weights from the Maxwell-Boltzmann distribution, showing a very good comparison with the experimental spectra. (C) 2020 Elsevier Ltd. All rights reserved.