Iron Dissolution from Goethite (α-FeOOH) Surfaces in Water by Ab Initio Enhanced Free-Energy Simulations

Dissolution of redox-active metal oxides plays a key role in a variety of phenomena, including (photo)electrocatalysis, degradation of battery materials, corrosion of metal oxides, and biogeochemical cycling of metals in natural environments. Despite its widespread significance, mechanisms of metal-oxide dissolution remain poorly understood on the atomistic level. This study is aimed at elucidating the long-standing problem of iron dissolution from Fe(III)-oxide, a complex process involving coupled hydrolysis, surface protonation, electron transfer, and metal–oxygen bond cleavage. We examine the case of goethite (α-FeOOH), a representative phase, bearing structural similarities with many other metal (hydr)oxides. By employing quantum molecular dynamics simulations (metadynamics combined with the Blue Moon ensemble approach), we unveil the mechanistic pathways and rates of both nonreductive and reductive dissolution of iron from the (110) and (021) goethite facets in aqueous solutions at room temperature. ...