Theoretical understanding of water adsorption on stepped iron surfaces

Abstract

Nanoscale zero-valent iron (nZVI) has attracted significant interest due to its high capability in groundwater remediation. Understanding the interaction between water and nZVI is essential to optimizing its performance. While stable stepped surfaces may play a unique role in nZVI during their practical applications due to their higher reactivity, the interactions between water and stepped surfaces are still rarely investigated. Here we applied density functional theory (DFT) to study the adsorption properties of water on stable stepped Fe(210) and Fe(211) surfaces with the consideration of the van der Waals correction. Our results revealed that the adsorption strength of molecular water is enhanced on surface Fe atoms with lower coordination numbers (CN). Accordingly, the water has a stronger interaction on the stepped surface after the dissociation into H and OH. The stepped surface can facilitate water dissociation by greatly reducing dissociation energy barriers. Since water adsorption and dissociation are the first stage of iron oxidation by water, our DFT results demonstrate that the water adsorption on stepped iron surface may determine the lifetime of nZVI. Our findings, therefore, suggests the passivation of stepped surface can be a practical approach to improve the performance of nZVI.