Molecular Dynamics Study of Fe(II) Adsorption, Electron Exchange, and Mobility at Goethite (α-FeOOH) Surfaces

Zarzycki, Piotr; Kerisit, Sebastien N.; Rosso, Kevin M.

doi:10.1021/jp511086r

Cited by 67 publications

(147 citation statements)

References 69 publications

(139 reference statements)

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“…71 Moreover, it should be noted that the presence of step edges could lead to the formation of adsorption sites with configurations and protonation states 72 distinct from those considered in this work and thus with different adsorption free energies. As described in detail in the next section, Fe(II) is bound to three doubly-coordinated hydroxyl groups when adsorbed as a tridentate innersphere complex.…”

Section: Fe(ii) Adsorptionmentioning

confidence: 78%

Computational Molecular Simulation of the Oxidative Adsorption of Ferrous Iron at the Hematite (001)–Water Interface

2015

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The interaction of Fe(II) with ferric oxide/oxyhydroxide phases is central to the biogeochemical redox chemistry of iron. Molecular simulation techniques were employed to determine the mechanisms and quantify the rates of Fe(II) oxidative adsorption at the hematite (001)-water interface. Molecular dynamics potential of mean force calculations of Fe(II) adsorbing on the hematite surface revealed the presence of three free energy minima corresponding to Fe(II) adsorbed in an outersphere complex, a monodentate innersphere complex, and a tridentate innersphere complex. The free energy barrier for adsorption from the outersphere position to the monodentate innersphere site was calculated to be similar to the activation enthalpy for water exchange around aqueous Fe(II). Adsorption at both innersphere sites was predicted to be unfavorable unless accompanied by release of protons. Molecular dynamics umbrella sampling simulations and ab initio cluster calculations were performed to determine the rates of electron transfer from Fe(II) adsorbed as an innersphere and outersphere complex. The electron transfer rates were calculated to range from 10 -4 to 10 2 s -1 , depending on the adsorption site and the Page 1 of 43 ACS Paragon Plus EnvironmentThe Journal of Physical Chemistry 2 potential parameter set, and were generally slower than those obtained in the bulk hematite lattice. The most reliable estimate of the rate of electron transfer from Fe(II) adsorbed as an outersphere complex to lattice Fe(III) was commensurate with the rate of adsorption as an innersphere complex suggesting that adsorption does not necessarily need to precede oxidation.

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Section: Fe(ii) Adsorptionmentioning

confidence: 78%

Computational Molecular Simulation of the Oxidative Adsorption of Ferrous Iron at the Hematite (001)–Water Interface

2015

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“…This hydrogen interacts with the FeOOH corrosion products to produce Fe3O4 (e.g., Figure F1) [19,83]:…”

Section: Fe 0 Corrosion Seriesmentioning

confidence: 99%

“…The absorption peaks associated with specific molecular species and ions at different wavelengths include: The Eh-pH relationships required by Equation (83) to produce ClO − were observed in trials E145, E146 ( Figures C19-C36). This indicates that the first stage in the desalination process involves O2, e.g., Figure C37ah ions have demonstrated that they assist in the formation of polymerized (polymeric) FeOOH structures [250].…”

Section: Appendix H Identification Of the Radicals Involved In Nacl mentioning

confidence: 99%

Desalination of Water Using ZVI (Fe0)

Antia¹

2015

Water

196

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Batch treatment of water (0.2 to 240 L) using Fe 0 (44,000-77,000 nm) in a diffusion environment operated (at −8 to 25 °C) using: (a) no external energy; (b) pressurized (<0.1 MPa) air; (c) pressurized (<0.1 MPa) acidic gas (CO2); (d) pressurized (<0.1 MPa) anoxic gas (N2); (e) pressurized (<0.1 MPa) anoxic, acidic, reducing gas (H2 + CO + CO2 + CH4 + N2), reduces the salinity of water. Desalination costs increase with increasing NaCl removal. The cost of reducing water salinity from: (i) 2.65 to 1.55 g·L . Desalination is accompanied by the removal, from the water, of one or more of: nitrate, chloride, fluoride, sulphate, phosphate, As, B, Ba, Ca, Cd, Co, Cu, Fe, Mg, Mn, Na, Ni, P, S, Si, Sr, Zn. The rate of desalination is enhanced by increasing temperatures and increasing HCO3 − /CO3 2− concentrations. The rate of desalination decreases with increasing SO4 2− removal under acidic, or pH neutral, operating conditions.

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“…This model has been tested using molecular simulations [41]. From these simulations the authors derive that electron injection from sorbed Fe(II) to surface-bound Fe(III) is energetically not favorable at some crystallographic faces.…”

Section: Electron Transfer At Ferric (Hydr)oxides Surfaces: the Role mentioning

confidence: 99%

Reductive Dissolution and Reactivity of Ferric (Hydr)oxides: New Insights and Implications for Environmental Redox Processes

Peiffer

Wan

2016

Iron Oxides

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Molecular Dynamics Study of Fe(II) Adsorption, Electron Exchange, and Mobility at Goethite (α-FeOOH) Surfaces

Cited by 67 publications

References 69 publications

Computational Molecular Simulation of the Oxidative Adsorption of Ferrous Iron at the Hematite (001)–Water Interface

Computational Molecular Simulation of the Oxidative Adsorption of Ferrous Iron at the Hematite (001)–Water Interface

Desalination of Water Using ZVI (Fe0)

Reductive Dissolution and Reactivity of Ferric (Hydr)oxides: New Insights and Implications for Environmental Redox Processes

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