Abstract
The adsorption of sodium dihydrogen phosphate (NaH2PO4) onto X- and Y-type faujasite zeolites was computationally studied using the Density Functional Theory (DFT) method. The structures were modeled using the Materials Studio software. The Si/Al ratios for the X- and Y-type zeolite models were 1.2 and 2.5, respectively. The central pore of the zeolite provided a more favorable coordination for adsorbing NaH2PO4. Full molecular optimization and adsorption energy calculations were performed using the VASP code. The adsorption was more effective on zeolite Y, with an adsorption energy of 161 kJ/mol, compared to the zeolite X system, with an adsorption energy of 31.64 kJ/mol. This calculated value for X-type faujasite was found in the interval of the adsorption energy of H2PO4− on hydrated Fe oxide (94.4 kJ/mol) and modified polyether sulfone (22.5 kJ/mol), and the calculated adsorption energy of the molecule on Y-type faujasite coincides with the reported value for this adsorbate on Mg/Ca-modified biochar structures. The molecular conformations of the adsorbate on the two studied models are very different, so the difference between the adsorption energy values of each type of zeolite model is comprehensible. On the one hand, the oxygen atoms of the molecule formed a bidentate complex with the hydrogen atoms of the pore in the X-type faujasite model, and the O-H distance was 1.5 Ǻ. On the other hand, an adsorbed oxygen atom of the phosphate was placed on a hydrogen atom at site II of the Y-type faujasite zeolite, and two of the hydrogen atoms of the phosphate were placed on the oxygen atoms. The Bader analysis results indicated that the negative charge of the phosphate anions was delocalized on the zeolites protons. The hydroxy groups of the phosphate form bonds between their hydrogen atoms and the oxygen atoms of the zeolite porous structure; therefore, we concluded that these sites have an alkaline character. The aim of this study was to include a computational analysis of possible phosphate adsorption mechanisms in faujasite zeolites that can be confirmed by experimental tests, and hence contribute to the generation of new technologies for capturing pollutant molecules in wastewater. The results are in agreement with the experimental information concerning the influence of pH on the adsorption activity of phosphate adsorption on zeolites.