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Variable Hydrogen Bond Strength in Akaganeite
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
2012 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 116, no 3, 2303-2312 p.Article in journal (Refereed) Published
Abstract [en]

Akaganeite (beta-FeOOH) is a chloride-bearing iron oxy-hydroxide with a hollandite-type structure. This high specific surface area mineral has been the object of numerous studies given its high reactivity and involvement in natural and industrial processes. The important ion exchange attributes of this mineral involve similar to 0.4 x 0.4 nm wide channels in which chloride ions are stabilized by hydrogen bonding from bulk OH groups. This work provides further details on the relationship between bulk chloride ion loadings and hydrogen bond strengths. Molecular dynamics calculations were first carried out on chloride-free and bearing lattices to build a conceptual model for possible interactions in the akaganeite bulk. Experimental work was thereafter carried out on synthetic acicular particles (7 x 80 to 11 x 110 nm) reacted to aqueous solutions of HCl, then dried under dry N-2(g). These samples were studied by Fourier transform infrared spectroscopy, temperature-programmed desorption, X-ray photoelectron spectroscopy, and X-ray powder diffraction as well as transmission electron spectroscopy. Results collectively show that Cl/Fe molar ratios increasing from 0.169 up to 0.442 induce important changes in the hydrogen bonding environment of bulk hydroxyls. This can specifically be seen through shifts in bulk O-H stretching frequencies from 3496/3395 to 3470/3350 cm(-1). These changes are associated with a substantial shortening of particle lengths (97 to 45 nm), expansion of crystallographic lattice size (up to 0.9%), and increases in median thermal dehydroxylation temperatures (260 to 305 degrees C). Our work thereby highlights important variations in physicochemical attributes of akaganeite particles reacted with HCl. Such variations should consequently be considered in settings involving submicrometer-sized akaganeite particles.

Place, publisher, year, edition, pages
Washington DC: American Ceramic Society, 2012. Vol. 116, no 3, 2303-2312 p.
National Category
Chemical Sciences
URN: urn:nbn:se:umu:diva-52653DOI: 10.1021/jp2097108ISI: 000299584400035OAI: diva2:506944
Available from: 2012-03-01 Created: 2012-02-28 Last updated: 2013-05-13Bibliographically approved
In thesis
1. Surface and Bulk Reactivity of Iron Oxyhydroxides: A Molecular Perspective
Open this publication in new window or tab >>Surface and Bulk Reactivity of Iron Oxyhydroxides: A Molecular Perspective
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Iron oxyhydroxide (FeOOH) mineral plays an important role in a variety of atmospheric, terrestrial and technological settings. Molecular resolution of reactions involving these minerals is thereby required to develop a fundamental understanding of their contributions in processes taking place in the atmosphere, Earth’s upper crust as well as the hydrosphere. This study resolves interactions involving four different types of synthetic FeOOH particles with distinct and well-defined surfaces, namely lath- and rod-shaped lepidocrocite (γ), goethite (α) and akaganéite (β). The surface and bulk reactivities of these particles are controlled by their distinct structures. When exposed to ambient atmospheric or aqueous conditions their surfaces are populated with different types of (hydr)oxo functional groups acting as reaction centers. These sites consist of hydroxyl groups that can be singly- (≡FeOH, -OH), doubly- (≡Fe2OH, μ-OH), or triply-coordinated (≡Fe3OH, μ3-OH) with underlying Fe atoms. Moreover, these sites exhibit different types, densities, distributions, as well as hydrogen bonding patterns on different crystal planes for each mineral. Knowledge of the types and distributions of hydroxyl groups on minerals with different surface structures is fundamental for building a molecular-scale understanding of processes taking place at FeOOH particle surfaces.

In this thesis, Fourier transform infrared (FTIR) spectroscopy was used to resolve the interactions between (hydr)oxo groups of FeOOH particles with (in)organic acids, salts, water vapor as well as carbon dioxide. The focus on such compounds was justified by their importance in natural environments. This thesis is based on 9 articles and manuscripts that can be found in the appendices.

FTIR spectroscopic signatures of hydroxyl groups in the bulk of well crystallized FeOOH minerals were characterized for structural differences and thermal stabilities. Those of akaganéite were particularly resolved for the variable bond strength of bulk hydroxyls induced by the incorporation of HCl through nanostructured channels at the terminations of the particles. FTIR bands of hydroxyl groups at all particle surfaces were monitored for responses to thermal gradients and proton loadings, providing experimental validation to previous theoretical accounts on surface site reactivity. This site reactivity was resolved further in the fluoride (F-) and phosphate (PO43-) ions adsorption study to follow the site selectivity for ligand-exchange reactions. These efforts showed that singly-coordinated groups are the primary adsorption centers for ligands, doubly-coordinated groups can only be exchanged at substantially higher ligand loadings, while triply coordinated groups are largely resilient to any ligand-exchange reaction.

These findings helped consolidate fundamental knowledge that can be used in investigating sorption processes involving atmospherically and geochemically important gases. The latter parts of this thesis were therefore focused on water vapor and carbon dioxide interactions with these FeOOH particles. These efforts showed how surface structure and speciation affect sorption loadings and configurations, as well as how water diffused into and through the akaganéite bulk. Hydrogen bonding is one of the most important forms of interactions between gas phase and minerals. It plays a crucial role in the formation of thin water films and in stabilizing surface (bi)carbonate species. The affinity of surface hydroxyl groups for water and carbon dioxide is strongly dependent on their abilities to form hydrogen bonds. These are controlled by coordination number and site accessibility/steric constraints. In agreement with the aforementioned ligand-exchange studies, surfaces dominated by singly coordinated groups have stronger ability to accumulate water layers than the ones terminated by groups of larger coordination number. Collectively, these efforts consolidate further the concept for structure-controlled reactivities in iron oxyhydroxides, and pave the way for new studies along such lines.

Place, publisher, year, edition, pages
Umeå: Umeå Universitet, 2013. 83 p.
Iron oxyhydroxide, adsorption, water, carbon dioxide, FTIR, molecular resolution
National Category
Physical Chemistry Inorganic Chemistry Geosciences, Multidisciplinary
urn:nbn:se:umu:diva-70289 (URN)978-91-7459-669-4 (printed) (ISBN)
Public defence
2013-06-05, KBC-huset, KB3B1, Umeå Universitet, Umeå, 13:00 (English)
Available from: 2013-05-13 Created: 2013-05-13 Last updated: 2013-05-15Bibliographically approved

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Song, XiaoweiBoily, Jean-Francois
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