Adsorption of Actinide (U–Pu) Complexes on the Silicene and Germanene Surface: A Theoretical Study

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2020-02, Vol.124 (8), p.1522-1534
• Main Authors: Grover, Payal, Ferch, Laura S, Schreckenbach, Georg
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.9b10888

Adsorption of actinide (Ac = U, Np, Pu) complexes with environmentally relevant ligands on silicene and germanene surfaces has been investigated using density functional theory to determine the geometrical, energetic, and electronic properties. Three types of ligands for each central metal atom are considered: OH–, NO3 –, and CO3 2– with common oxo ligands in all cases. Among these, carbonate complexes show the strongest adsorption followed by hydroxide and nitrate. Two types of model, cluster and periodic models, have been considered to include the short- and long-range effects. The cluster and periodic models are complementary, although the former has not yet been widely used for studies of 2D materials. Two cluster sizes have been investigated to check size dependency. Calculations were performed in the gas phase and water solvent. On the basis of the adsorption energy, for the CO3 2– and OH– ligands, the bond position between two Si atoms in the silicene sheet is the most strongly adsorbed site in the cluster model for silicene whereas in the periodic model these complexes exhibit strong binding on the Si atom of the silicene surface. The Ac complexes with the NO3 – ligand show strong affinity at the hollow space at the center of a hexagonal ring of silicene in both models. The H site is most favorable for the binding of complexes on the germanene cluster whereas these sites vary in the periodic model. Electronic structure calculations have been performed that show a bandgap range from 0.130 to 0.300 eV for the adsorption of actinide complexes on silicene that can be traced to charge transfer. Density of states calculations show that the contribution of the nitrate complexes is small near the Fermi level, but it is larger for the carbonate complexes in the silicene case. Strong interactions between Ac complexes and silicene are due to the formation of strong Si–O bonds upon adsorption which results in reduction of the actinide atom. Such bonding is lacking in germanene.