The Doping Effect of 13-Atom Iron Clusters on Water Adsorption and O-H Bond Dissociation

Understanding the interactions between water and Fe-based clusters is necessary to unravel the micromechanics of the surface hydrophilic property and the corrosion process of iron-related materials. Herein, a theoretical study is conducted of water adsorption and dissociation on icosahedral Fe₁₃ and Fe₁₂X (X = Ti, V, Cr, Mn, Co, Ni) clusters. It is found that the doping atoms have significant influence on the geometric structures, magnetic moments, and electronic states of Fe₁₂X clusters. The center-doped clusters X@Fe₁₂ show higher stability than the shell-doped X-Fe₁₂; Ni@Fe₁₂ exhibits lower activation energy for the dissociation of H₂O than all the others; Ti@Fe₁₂ strikes a weak bonding energy and high activation energy for water dissociation. Also, a water dimer finds a decreased energy barrier for O-H dissociation, and the electronic states and metal-water interactions can be altered by the support effect. This information is helpful to those working on water chemistry, anticorrosion wading devices, and high-standard potable water utilization.