Abstract
Goethite widely exists among ocean sediments; it plays an important role in fixing heavy metals and adsorbing organic contaminants. So the understanding of the adsorbing process of water molecule on its surface will be very helpful to further reveal such environmental friendly processes. The configuration, electronic properties and interaction energy of water molecules adsorbed on pnma goethite (010) surface were investigated in detail by using density functional theory on 6-31G (d,p) basis set and projector- augment wave (PAW) method. The mechanism of the interaction between goethite surface and H2O was proposed. Despite the differences in total energy, there are four possible types of water molecule adsorption configurations on goethite (010) surface (Aa, Ab, Ba, Bb), forming coordination bond with surface Fe atom. Results of theoretical modeling indicate that the dissociation process of adsorbed water is an endothermic reaction with high activation energy. The dissociation of adsorbed water molecule is a proton transportation process between water’s O atoms and surface. PDOS results indicate that the bonding between H2O and (010) surface is due to the overlapping of water’s 2p orbitals and Fe’s 3d orbitals. These results clarify the mechanism on how adsorbed water is dissociated on the surface of goethite and potentially provide useful information of the surface chemistry of goethite.
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Alvarez, M., Tufo, A. E., Zenobi, C., Ramos, C. P., and Sileo, E. E., 2015. Chemical, structural and hyperfine characterization of goethites with simultaneous incorporation of manganese, cobalt and aluminum ions. Chemical Geology, 414: 16–27.
Aquino, A. J. A., Tunega, D., Haberhauer, G., Gerzabek, M. H., and Lischka, H., 2007. Quantum chemical adsorption studies on the (110) surface of the mineral goethite. Journal of Physical Chemistry C, 111: 877–885.
Brown, I. D., 2002. The Chemical Bond in Inorganic Chemistry: The Valonce Bond Model. Oxforf University Press, New York, 12–15.
Brümmer, G. W., Barrow, N. J., and Fischer, L., 2013. Effect of porosity of goethite on the sorption of six heavy metal ions. European Journal of Soil Science, 64: 805–813.
Coey, J., Barry, A., Brotto, J., Rakoto, H., Brennan, S., Mussel, W. N., Collomb, A., and Fruchart, D., 1995. Spin flop in goethite. Journal of Physics-Condensed Matter, 7: 759–768.
Gualtieri, A. F., and Venturelli, P., 1999. In situ study of the goethite-hematite phase transformation by real time synchrotron powder diffraction. American Mineralogist, 84: 895–904.
Kanel, S. R., Neppolian, B., Jung, H. Y., and Choi, H., 2004. Comparative removal of polycyclic aromatic hydrocarbons using iron oxide and hydrogen peroxide in soil slurries. Environmental Engineering Science, 21: 741–751.
Kubicki, J. D., Paul, K. W., and Sparks, D. L., 2008. Periodic density functional theory calculations of bulk and the (010) surface of goethite. Geochemical Transactions, 9.
Nora, J. D. L., and Cooper, T. G., 2007. Surface simulation studies of the hydration of white rust Fe(OH)2, goethite a-FeO(OH) and hematite a-Fe2O3. Geochimica et Cosmochimica Acta, 71: 1655–1673.
Otte, K., Schmahl, W. W., and Pentcheva, R., 2012. Density functional theory study of water adsorption on FeOOH surfaces. Surface Science, 606: 1623–1632.
Rakovan, J., Becker, U., and Hochella, M. F., 1999. Aspects of goethite surface microtopography, structure, chemistry, and reactivity. American Mineralogist, 84: 884–894.
Rustad, J. R., and BoiLy, J., 2010. Density functional calculation of the infrared spectrum of surface hydroxyl groups on goethite (a-FeOOH). American Mineralogist, 95: 414–417.
Sheals, J., Sjoberg, S., and Persson, P., 2002. Adsorption of glyphosate on goethite: Molecular characterization of surface complexes. Environmental Science & Technology, 36: 3090–3095.
Stemig, A. M., Tram, A. D., Yuwono, V. M., Arnold, W. A., and Penn, R. L., 2014. Goethite nanoparticle aggregation: Effects of buffers, metal ions, and 4-chloronitrobenzene reduction. Environmental Science-Nano, 1: 478–487.
Thien, A. V., Reagan, M. M., Li, D., Legg, B., Yoreo, J. J. D., Banfield, J. F., and Zhang, H., 2014. Kinetics of crystal growth of nanogoethite in aqueous solutions containing nitrate and sulfate anions. CrystEngComm, 16: 1466–1471.
Whitehead, C. F., Carbonaro, R. F., and Stone, A. T., 2015. Adsorption of benzoic acid and related carboxylic acids onto FeOOH (goethite): The low ionic strength regime. Aquatic Geochemistry, 21: 99–121.
Xi, J., He, M., Wang, K., and Zhang, G., 2013. Adsorption of antimony (III) on goethite in the presence of competitive anions. Journal of Geochemical Exploration, 132: 201–208.
Xu, J. H., Jarlborg, T., and Freeman, A. J., 1989. Self-consistent band structure of the rutile dioxides NbO2, RuO2, and IrO2. Physical Review B Condensed Matter, 11: 7939–7947.
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Xiu, F., Zhou, L., Xia, S. et al. Adsorption mechanism of water molecule on goethite (010) surface. J. Ocean Univ. China 15, 1021–1026 (2016). https://doi.org/10.1007/s11802-016-3171-x
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DOI: https://doi.org/10.1007/s11802-016-3171-x