Density Functional Theory Simulation Study on the Hydroxylated Hematite Surfaces: Understanding its Reactivity

"The hematite surface plays a vital role in several processes of industrial and technological importance, such as, in beneficiation of iron ores, catalysis, and geochemical processes. Therefore, it is imperative to have a clear description of the structure and composition of this surface, which forms the underlying basis for such a wide variety of complex phenomena. Particularly, from the perspective of beneficiation of Indian alumina-rich iron ore slimes and fines, a clear understanding of the surface structure and composition of hematite surface and its difference from the alumina surface will facilitate identification and/or design of selective reagents which can be used to separate the two minerals. In this work, the hydroxylated hematite (0001) surface was modeled using density functional theory (DFT). The computed planar relaxations are consistent with X-Ray crystal truncation rod diffraction results reported in the literature. It is demonstrated that only one type of surface, that is, the (OH)3-Fe-H3O3-R is stable under aqueous conditions, as the relaxations for the second type of termination: (OH)3-Fe-Fe-R do not match quantitatively with experiments suggesting that its coexistence with the (OH)3-Fe-H3O3-R surface is unlikely. A detailed analysis of this surface shows that two of the three (OH) groups are not connected to the Fe surface atom. Instead, they form H2O molecules by combining with the H-atoms on the O-layer beneath the Fe-terminated surface leaving the Fe surface-atom bonded to only one OH-group. This undercoordination of Fe-atoms on the surface explains its higher reactivity as compared to hydroxylated alumina.INTRODUCTIONThe hematite surface plays a vital role in several processes of industrial and technological importance. A few examples are: flocculation/froth flotation of iron ores (Ravishankar, Pradip & Khosla, 1995), catalysis (Muhler, Schlögl & Ertl, 1992; Samsonov, 1973), and geochemical processes (Brown, Henrich, Casey, Clark, Eggleston & Felmy et al., 1999; Sposito, 1989). Therefore, it is imperative to have a clear description of the structure and composition of the hematite surface, which form the underlying basis for such a wide variety of complex phenomena. Particularly, from the perspective of beneficiation of Indian alumina-rich iron ore slimes and fines, this is an important problem, as a clear understanding of the surface structure and composition of hematite surface and its difference from the alumina surface will facilitate identification and/or design of selective reagents which can be used to separate the two minerals. Our current research focus is at employing molecular modeling techniques to come up with such selective reagents and then test their efficacy in the practical scenario through selective dispersion – flocculation labscale experiments and subsequently plant trials. Obviously, the correct structure and composition of the hydroxylated hematite surface is a fundamental prerequisite for such investigations."