Adsorption and diffusion of actinyls on the basal gibbsite (001) surface: a theoretical perspective†

Actinides are an important component of nuclear fuel for nuclear power and affect human health, and a key process in the transport of radionuclides in the environment is adsorption on mineral surfaces. In this work, we have used density functional theory (DFT) to investigate the microscopic adsorption and diffusion mechanisms of actinyls, U(V), U(VI), Np(V), Np(VI) Pu(V), and Pu(VI), on the gibbsite (001) surface. Actinyls(VI) are attached to the gibbsite surface through two An–O_s bonds, which results in a bidentate inner sphere mode, while actinyls(V) favor a monodentate inner sphere adsorption mode with the gibbsite (001) surface. The solvent effects were considered through an explicit water cluster model. All the actinyls studied can be efficiently adsorbed on the gibbsite (001) surface with binding energies ranging from −113.9 kJ mol⁻¹ to −341.2 kJ mol⁻¹. Electronic structure analyses indicate that the cooperation of the An–O_s bonds and hydrogen bonds leads to high adsorption stability of the actinyls with the gibbsite surface. The diffusion barriers of the actinyls on the gibbsite surface were determined, and the high energy barriers indicate that this type of gas-phase diffusion process is not likely to take place.