Adsorption characteristics of silver atoms and silver ions on silica surface in silver nanoparticle hydrosol system

Abstract Previous studies have demonstrated that silver ions (Ag+) can be released from silver nanoparticles (AgNPs) to produce a system of silver atoms (Ag0) and Ag+ in equilibrium, which may affect the environment through adsorption on sediment. Here, the adsorption behaviour of Ag0 and Ag+ in a AgNP hydrosol system on a silica surface was systematically investigated using experimental evaluation and first-principles calculations based on density functional theory. The adsorption environment and performance were first analysed by batch and fixed-bed experiments, which indicated that less adsorption occurred between silica and silver. Subsequent energy calculations and structural optimisation revealed that both Ag0 and Ag+ were more likely to be chemisorbed on the silica surface through covalent (Ag O) bonds. The average adsorption energies of SiO2/Ag+ and SiO2/Ag0 were −5.445 and −3.61 eV, respectively. In addition, Ag0 lost an average of 0.86 electrons to the O4–silica bond. By contrast, only a few electrons, which bonded with O1, were transferred from silica to Ag+. Analyses of the density of states and crystal orbital Hamilton population revealed that O and Ag were hybridised with the 2p–4d orbitals after adsorption. In addition, the peak shifts in the high-resolution Ag 3d, O 1s and Si 2p X-ray photoelectron spectra after adsorption revealed changes in the chemical state. The presence of Ag O bonds was confirmed by the surface-enhanced Raman scattering spectrum. Silica was selected as the main component of sediment in this study, and it is hoped that this work will motivate a simulation of the migration and transformation of silver by sediment in the water environment.