Ab initio modeling of Fe(ii) adsorption and interfacial electron transfer at goethite (α-FeOOH) surfaces

Abstract

Goethite (α-FeOOH) surfaces represent one of the most ubiquitous redox-active interfaces in the environment, playing an important role in biogeochemical metal cycling and contaminant residence in the subsurface. Fe(II)-catalyzed recrystallization of goethite is a fundamental process in this context, but the proposed Fe(II)_aq–Fe(III)_goethite electron and iron atom exchange mechanism of recrystallization remains poorly understood at the atomic level. We examine the adsorption of aqueous Fe(II) and subsequent interfacial electron transfer (ET) between adsorbed Fe(II) and structural Fe(III) at the (110) and (021) goethite surfaces using density functional theory calculations including Hubbard U corrections (DFT + U) aided by ab initio molecular dynamics simulations. We investigate various surface sites for the adsorption of Fe²⁺(H₂O)₆ in different coordination environments. Calculated energies for adsorbed complexes at both surfaces favor monodentate complexes with reduced 4- and 5-fold coordination over higher-dentate structures and 6-fold coordination. The hydrolysis of H₂O ligands is observed for some pre-ET adsorbed Fe(II) configurations. ET from the adsorbed Fe(II) into the goethite lattice is calculated to be energetically uphill always, but simultaneous proton transfer from H₂O ligands of the adsorbed complexes to the surface oxygen species stabilizes post-ET states. We find that surface defects such as oxygen vacancies near the adsorption site also can stabilize post-ET states, enabling the Fe(II)_aq–Fe(III)_goethite interfacial electron transfer reaction implied from experiments to proceed.