期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 119, 期 6, 页码 3111-3123出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp511086r
关键词
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资金
- Geosciences Research Program in the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences
- Ministry of Science and Higher Education [MNiSW IP2012 059872]
- DOE's Office of Biological and Environmental Research
We present classical molecular simulations of the adsorption free energy profiles for the aqueous Fe(II) ion approaching key low index crystal faces of goethite at neutral surface charge conditions. Calculated profiles show minima corresponding to stable outer- and inner-sphere adsorbed structures. We analyzed the energetics and kinetics of most possible interfacial electron transfer reactions, as well as analyzing the same for subsurface migration pathways of injected electrons through calculating the Marcus free energy surfaces. We conclude that inner-sphere Fe(II)-complex formation is required for the interfacial electron transfer to occur, but the energetic cost of moving from the outer-sphere to inner-sphere geometry may prevent electron injection at some faces. We also show that some surfaces, especially (101), (100) and (001), are more energetically prone toward reduction than others. We demonstrate that subsurface charge migration in directions parallel to the surface, which run along the iron chains, is more energetically plausible than conduction through the resistive crystal bulk phase. Collectively this leads to the conclusion that Fe(II)-catalyzed recrystallization of goethite most likely proceeds by short path length electron migration through specific goethite surfaces along specific directions, until capture at Fe sites structurally susceptible to reduction and release.
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