Density functional theory based studies on the adsorption of rare-earth ions from hydrated nitrate salt solutions on...

This article represents density functional theory (DFT) based comparative analysis on six trivalent rare-earth ions (RE³⁺; RE: Y, La, Ce, Sm, Eu and Gd) absorption, from the respective nitrate-hexahydrate salts, on graphitic carbon nitride (g-C₃N₄) 2D monolayer, and the photocatalytic properties of the RE³⁺ adsorbed g-C₃N₄ systems (g-C₃N₄/RE³⁺) based on the ground-state electronic structure calculations. Structure, stability and coordination chemistry of two configurations of each hydrated RE-salt system are discussed in detail. Both DFT (B3LYP/SDD) and semi-empirical (Sparkle/PM7) calculations identify the central N₆ vacancy of pristine g-C₃N₄ as the most suitable site for RE³⁺ adsorption. Bader's QTAIM, Mayer bond order and charge population analyses (ADCH, CHELPG and DDEC) are performed to describe the bond characteristics within the systems under study. Thermochemical calculations suggest that the adsorption process is thermodynamically more feasible for higher atomic number (Z) RE³⁺ [Sm³⁺, Eu³⁺ and Gd³⁺], compared to lower-Z RE³⁺ [Y³⁺, La³⁺ and Ce³⁺] ions. Besides, the better photocatalytic properties of higher-Z RE³⁺ adsorbed g-C₃N₄ systems are revealed from better HOMO-LUMO delocalization, decreased HOMO-LUMO gap, increased softness, higher electrophilicity and electron transfer parameter, compared to pristine or lower-Z RE³⁺ adsorbed g-C₃N₄ systems, as obtained from Hirshfeld orbital compositions, density of states and condensed Fukui function analyses.