Surface Charge Effects on Fe(II) Sorption and Oxidation at (110) Goethite Surfaces

Zarzycki, Piotr; Rosso, Kevin M.

doi:10.1021/acs.jpcc.8b02099

Surface Charge Effects on Fe(II) Sorption and Oxidation at (110) Goethite Surfaces

Journal Article · Wed Apr 18 00:00:00 EDT 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b02099· OSTI ID:1509676

^[1]; ^[2]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Geosciences Division
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Iron(III) oxides and oxyhydroxides are among the most reactive minerals in the environment, with surfaces that become charged when immersed in water. The governing role of surface charge over interfacial processes such as metal sorption is well understood. However, its role in interfacial redox reactions, such as when metal sorption is coupled to interfacial electron transfer (ET), is not. This is mainly because surface charge affects not only the types and densities of surface complexes formed but also their respective driving forces for ET. An important case is Fe(II)-catalyzed recrystallization of Fe(III)-oxyhydroxides, in which Fe(II) sorption and interfacial ET are closely linked. We used replica-exchange constant-pH molecular dynamics simulations (Zarzycki, P.; Smith, D. M.; Rosso, K. M. J. Chem. Theory Comput. 2015, 11, 1715–1724) to calculate the distance-dependent electrostatic potential at charged (110) surfaces of goethite particles, assessing its effect on previously computed Fe(II) sorption and interfacial ET free energies (Zarzycki, P.; Kerisit, S.; Rosso, K. M. J. Phys. Chem. C 2015, 119, 3111–3123). We show that Fe(II) adsorbs preferentially as an inner-sphere complex on the negatively charged surface, and as an outer-sphere complex on the positively charged surface because of both electrostatic repulsion and high energy barriers that arise from ordered water layers at the interface. The separation distance between adsorbed Fe(II) and the surface largely dictates adiabatic versus nonadiabatic ET regimes for this interface. The findings help unravel the pH dependence of Fe(II)-catalyzed recrystallization of goethite.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1509676

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 18 Vol. 122; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

The Iron Oxides Cornell, R. M.; Schwertmann, U. https://doi.org/10.1002/3527602097	book	July 2003
Charge and Energy Transfer Dynamics in Molecular Systems May, Volkhard; Kühn, Oliver Wiley-VCH Verlag GmbH & Co. KGaA https://doi.org/10.1002/9783527633791	book	February 2011
Constant pH molecular dynamics in generalized Born implicit solvent Mongan, John; Case, David A.; McCammon, J. Andrew Journal of Computational Chemistry, Vol. 25, Issue 16 https://doi.org/10.1002/jcc.20139	journal	December 2004
Intrinsic Proton Affinity of Reactive Surface Groups of Metal (Hydr)oxides: The Bond Valence Principle Hiemstra, T.; Venema, P.; Riemsdijk, W. H. Van Journal of Colloid and Interface Science, Vol. 184, Issue 2 https://doi.org/10.1006/jcis.1996.0666	journal	December 1996
Molecular Dynamics Study of Proton Binding to Silica Surfaces Rustad, James R.; Wasserman, Evgeny; Felmy, Andrew R. Journal of Colloid and Interface Science, Vol. 198, Issue 1 https://doi.org/10.1006/jcis.1997.5195	journal	February 1998
Intrinsic Proton Affinity of Reactive Surface Groups of Metal (Hydr)oxides: Application to Iron (Hydr)oxides Venema, Peter; Hiemstra, Tjisse; Weidler, Peter G. Journal of Colloid and Interface Science, Vol. 198, Issue 2 https://doi.org/10.1006/jcis.1997.5245	journal	February 1998
Electron transfer in environmental systems: a frontier for theoretical chemistry Rosso, Kevin M.; Dupuis, Michel Theoretical Chemistry Accounts, Vol. 116, Issue 1-3 https://doi.org/10.1007/s00214-005-0016-x	journal	October 2005
Complexation of carbonate species at the goethite surface: Implications for adsorption of metal ions in natural waters van Geen, Alexander; Robertson, Alexander P.; Leckie, James O. Geochimica et Cosmochimica Acta, Vol. 58, Issue 9 https://doi.org/10.1016/0016-7037(94)90286-0	journal	May 1994
A molecular dynamics study of solvated orthosilicic acid and orthosilicate anion using parameterized potentials Rustad, James R.; Hay, Benjamin P. Geochimica et Cosmochimica Acta, Vol. 59, Issue 7 https://doi.org/10.1016/0016-7037(95)00041-w	journal	April 1995
Molecular layering of water in thin films between mica surfaces and its relation to hydration forces Pashley, Richard M.; Israelachvili, Jacob N. Journal of Colloid and Interface Science, Vol. 101, Issue 2 https://doi.org/10.1016/0021-9797(84)90063-8	journal	October 1984
Molecular dynamics simulation of adsorption in electric double layers Philpott, Michael R.; Glosli, James N.; Zhu, Sheng-Bai Surface Science, Vol. 335 https://doi.org/10.1016/0039-6028(95)00456-4	journal	July 1995
Comparison of the Monte Carlo estimation of surface electrostatic potential at the hematite (0 0 0 1)/electrolyte interface with the experiment Zarzycki, Piotr Applied Surface Science, Vol. 253, Issue 18 https://doi.org/10.1016/j.apsusc.2007.03.064	journal	July 2007
Modules based on the geochemical model PHREEQC for use in scripting and programming languages Charlton, Scott R.; Parkhurst, David L. Computers & Geosciences, Vol. 37, Issue 10 https://doi.org/10.1016/j.cageo.2011.02.005	journal	October 2011
The influence of edge sites on the development of surface charge on goethite nanoparticles: A molecular dynamics investigation Rustad, James R.; Felmy, Andrew R. Geochimica et Cosmochimica Acta, Vol. 69, Issue 6 https://doi.org/10.1016/j.gca.2004.08.030	journal	March 2005
Computer simulation of electron transfer at hematite surfaces Kerisit, Sebastien; Rosso, Kevin M. Geochimica et Cosmochimica Acta, Vol. 70, Issue 8 https://doi.org/10.1016/j.gca.2005.12.021	journal	April 2006
Adsorption and surface oxidation of Fe(II) on metal (hydr)oxides Hiemstra, Tjisse; van Riemsdijk, Willem H. Geochimica et Cosmochimica Acta, Vol. 71, Issue 24 https://doi.org/10.1016/j.gca.2007.09.030	journal	December 2007
Water structure at hematite–water interfaces Kerisit, Sebastien Geochimica et Cosmochimica Acta, Vol. 75, Issue 8 https://doi.org/10.1016/j.gca.2011.01.026	journal	April 2011
Absolute acidity of clay edge sites from ab-initio simulations Tazi, Sami; Rotenberg, Benjamin; Salanne, Mathieu Geochimica et Cosmochimica Acta, Vol. 94 https://doi.org/10.1016/j.gca.2012.07.010	journal	October 2012
Acidity of edge surface sites of montmorillonite and kaolinite Liu, Xiandong; Lu, Xiancai; Sprik, Michiel Geochimica et Cosmochimica Acta, Vol. 117 https://doi.org/10.1016/j.gca.2013.04.008	journal	September 2013
Adsorption of heavy metal ions on soils and soils constituents Bradl, Heike B. Journal of Colloid and Interface Science, Vol. 277, Issue 1 https://doi.org/10.1016/j.jcis.2004.04.005	journal	September 2004
Nonlinear response of the surface electrostatic potential formed at metal oxide/electrolyte interfaces. A Monte Carlo simulation study Zarzycki, Piotr; Rosso, Kevin M. Journal of Colloid and Interface Science, Vol. 341, Issue 1 https://doi.org/10.1016/j.jcis.2009.09.002	journal	January 2010
Mineral surface charge development in mixed electrolyte solutions Kozin, Philipp A.; Boily, Jean-François Journal of Colloid and Interface Science, Vol. 418 https://doi.org/10.1016/j.jcis.2013.11.056	journal	March 2014
Biomolecular simulations at constant pH Mongan, John; Case, David A. Current Opinion in Structural Biology, Vol. 15, Issue 2 https://doi.org/10.1016/j.sbi.2005.02.002	journal	April 2005
Effects of different crystal faces on the surface charge of colloidal goethite (α-FeOOH) particles: an experimental and modeling study Gaboriaud, Fabien; Ehrhardt, Jean-Jacques Geochimica et Cosmochimica Acta, Vol. 67, Issue 5 https://doi.org/10.1016/s0016-7037(02)00988-2	journal	March 2003
Computer simulation of the structure of the electrochemical double layer Spohr, E. Journal of Electroanalytical Chemistry, Vol. 450, Issue 2 https://doi.org/10.1016/s0022-0728(97)00651-7	journal	June 1998
Anisotropic Morphological Changes in Goethite during Fe ²⁺ -Catalyzed Recrystallization Joshi, Prachi; Gorski, Christopher A. Environmental Science & Technology, Vol. 50, Issue 14 https://doi.org/10.1021/acs.est.6b00702	journal	July 2016
Stochastic Simulation of Isotopic Exchange Mechanisms for Fe(II)-Catalyzed Recrystallization of Goethite Zarzycki, Piotr; Rosso, Kevin M. Environmental Science & Technology, Vol. 51, Issue 13 https://doi.org/10.1021/acs.est.7b01491	journal	June 2017
Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms Brown, Gordon E.; Henrich, Victor E.; Casey, William H. Chemical Reviews, Vol. 99, Issue 1 https://doi.org/10.1021/cr980011z	journal	January 1999
Proton Dynamics on Goethite Nanoparticles and Coupling to Electron Transport Zarzycki, Piotr; Smith, Dayle M.; Rosso, Kevin M. Journal of Chemical Theory and Computation, Vol. 11, Issue 4 https://doi.org/10.1021/ct500891a	journal	March 2015
Fe(II)-Catalyzed Recrystallization of Goethite Revisited Handler, Robert M.; Frierdich, Andrew J.; Johnson, Clark M. Environmental Science & Technology, Vol. 48, Issue 19 https://doi.org/10.1021/es503084u	journal	September 2014
Atom Exchange between Aqueous Fe(II) and Goethite: An Fe Isotope Tracer Study Handler, Robert M.; Beard, Brian L.; Johnson, Clark M. Environmental Science & Technology, Vol. 43, Issue 4 https://doi.org/10.1021/es802402m	journal	February 2009
The missing term in effective pair potentials Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P. The Journal of Physical Chemistry, Vol. 91, Issue 24 https://doi.org/10.1021/j100308a038	journal	November 1987
Microscopic examination of free-energy relationships for electron transfer in polar solvents Hwang, Jenn Kang; Warshel, Arieh Journal of the American Chemical Society, Vol. 109, Issue 3 https://doi.org/10.1021/ja00237a013	journal	February 1987
Molecular Dynamics Simulation of the AgCl/Electrolyte Interfacial Capacity Zarzycki, Piotr; Rosso, Kevin M. The Journal of Physical Chemistry C, Vol. 114, Issue 21 https://doi.org/10.1021/jp100074h	journal	May 2010
Molecular Dynamics Study of Fe(II) Adsorption, Electron Exchange, and Mobility at Goethite (α-FeOOH) Surfaces Zarzycki, Piotr; Kerisit, Sebastien; Rosso, Kevin M. The Journal of Physical Chemistry C, Vol. 119, Issue 6 https://doi.org/10.1021/jp511086r	journal	January 2015
Computational Molecular Simulation of the Oxidative Adsorption of Ferrous Iron at the Hematite (001)–Water Interface Kerisit, Sebastien; Zarzycki, Piotr; Rosso, Kevin M. The Journal of Physical Chemistry C, Vol. 119, Issue 17 https://doi.org/10.1021/jp512422h	journal	April 2015
Molecular Dynamics Study of the Electrical Double Layer at Silver Chloride−Electrolyte Interfaces Zarzycki, Piotr; Kerisit, Sebastien; Rosso, Kevin M. The Journal of Physical Chemistry C, Vol. 114, Issue 19 https://doi.org/10.1021/jp9118666	journal	April 2010
Solvent-Induced Proton Hopping at a Water–Oxide Interface Tocci, Gabriele; Michaelides, Angelos The Journal of Physical Chemistry Letters, Vol. 5, Issue 3 https://doi.org/10.1021/jz402646c	journal	January 2014
Electrostatic Potential of Specific Mineral Faces Zarzycki, P.; Chatman, S.; Preočanin, T. Langmuir, Vol. 27, Issue 13 https://doi.org/10.1021/la201369g	journal	July 2011
Origin of 1-p K and 2-p K Models for Ionizable Water−Solid Interfaces Borkovec, Michal Langmuir, Vol. 13, Issue 10 https://doi.org/10.1021/la9621325	journal	May 1997
Effect of Different Crystal Faces on Experimental Interaction Force and Aggregation of Hematite Hiemstra, Tjisse; Van Riemsdijk, Willem H. Langmuir, Vol. 15, Issue 23 https://doi.org/10.1021/la9903604	journal	November 1999
Role of hydration and water structure in biological and colloidal interactions Israelachvili, Jacob; Wennerström, Håkan Nature, Vol. 379, Issue 6562 https://doi.org/10.1038/379219a0	journal	January 1996
An ab initio model of electron transport in hematite (α-Fe₂O₃) basal planes Rosso, Kevin M.; Smith, Dayle M. A.; Dupuis, Michel The Journal of Chemical Physics, Vol. 118, Issue 14, p. 6455-6466 https://doi.org/10.1063/1.1558534	journal	April 2003
Synchronization of trajectories in canonical molecular-dynamics simulations: Observation, explanation, and exploitation Uberuaga, Blas P.; Anghel, Marian; Voter, Arthur F. The Journal of Chemical Physics, Vol. 120, Issue 14 https://doi.org/10.1063/1.1667473	journal	April 2004
Charge transport in metal oxides: A theoretical study of hematite α-Fe2O3 Iordanova, N.; Dupuis, M.; Rosso, K. M. The Journal of Chemical Physics, Vol. 122, Issue 14 https://doi.org/10.1063/1.1869492	journal	April 2005
Molecular dynamics with coupling to an external bath Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F. The Journal of Chemical Physics, Vol. 81, Issue 8 https://doi.org/10.1063/1.448118	journal	October 1984
Simulation of the dynamics of electron transfer reactions in polar solvents: Semiclassical trajectories and dispersed polaron approaches Warshel, Arieh; Hwang, Jenn‐Kang The Journal of Chemical Physics, Vol. 84, Issue 9 https://doi.org/10.1063/1.449981	journal	May 1986
Molecular model for aqueous ferrous–ferric electron transfer Kuharski, Robert A.; Bader, Joel S.; Chandler, David The Journal of Chemical Physics, Vol. 89, Issue 5 https://doi.org/10.1063/1.454929	journal	September 1988
Investigation of the free energy functions for electron transfer reactions King, Gregory; Warshel, Arieh The Journal of Chemical Physics, Vol. 93, Issue 12 https://doi.org/10.1063/1.459255	journal	December 1990
A polarizable, dissociating molecular dynamics model for liquid water Halley, J. W.; Rustad, James R.; Rahman, A. The Journal of Chemical Physics, Vol. 98, Issue 5 https://doi.org/10.1063/1.465046	journal	March 1993
An analysis of the accuracy of Langevin and molecular dynamics algorithms Pastor, Richard W.; Brooks, Bernard R.; Szabo, Attila Molecular Physics, Vol. 65, Issue 6 https://doi.org/10.1080/00268978800101881	journal	December 1988
Oxide/water interfaces: how the surface chemistry modifies interfacial water properties Gaigeot, Marie-Pierre; Sprik, Michiel; Sulpizi, Marialore Journal of Physics: Condensed Matter, Vol. 24, Issue 12 https://doi.org/10.1088/0953-8984/24/12/124106	journal	March 2012
Electron transfer reactions in chemistry. Theory and experiment Marcus, Rudolph A. Reviews of Modern Physics, Vol. 65, Issue 3, p. 599-610 https://doi.org/10.1103/revmodphys.65.599	journal	July 1993
The Spatial Structure in Liquid Water Kusalik, P. G.; Svishchev, I. M. Science, Vol. 265, Issue 5176 https://doi.org/10.1126/science.265.5176.1219	journal	August 1994
Surface Charging and Points of Zero Charge Kosmulski, Marek https://doi.org/10.1201/9781420051896	book	January 2009

Cited By (1)

Lateral water structure connects metal oxide nanoparticle faces Zarzycki, Piotr; Colla, Christopher A.; Gilbert, Benjamin Journal of Materials Research, Vol. 34, Issue 3 https://doi.org/10.1557/jmr.2018.478	journal	January 2019

Similar Records

Ab Initio Modeling of Fe(II) Adsorption and Interfacial Electron Transfer at Goethite (α-FeOOH) Surfaces

Journal Article · Wed Dec 31 23:00:00 EST 2014 · Physical Chemistry Chemical Physics. PCCP, 17(22):14518-14531 · OSTI ID:1208706

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

Journal Article · Wed Feb 11 23:00:00 EST 2015 · Journal of Physical Chemistry C, 119(6):3111-3123 · OSTI ID:1184977

2015 Progress Report/July 2016: Iron Oxide Redox Transformation Pathways: The Bulk Electrical Conduction Mechanism

Technical Report · Mon Jul 25 00:00:00 EDT 2016 · OSTI ID:1271183

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Surface Charge Effects on Fe(II) Sorption and Oxidation at (110) Goethite Surfaces

Citation Formats

References (55)

Cited By (1)

Similar Records

Related Subjects