Water Ordering on the Magnetite Fe3O4 Surfaces

The interaction of water with the most prominent surfaces of Fe3O4, (001) and (111), is directly compared using a combination of temperature-programmed desorption, temperature-programmed low energy electron diffraction (TP LEED), and scanning probe microscopies. Adsorption on the (√2 × √2)R45°-reconstructed surface of Fe3O4(001) is strongly influenced by the surface reconstruction, which remains intact at all coverages. Close to the completion of the first monolayer, however, the ad-layer adopts a longer-range (2 × 2) superstructure. This finding is discussed in the context of a similar (2 × 2) superstructure recently observed on the (111) facet, which exists over a significantly larger range of temperatures and coverages. In both cases, the long-range order is evidence that water–water interactions exert a significant influence on the structure already prior to the nucleation of the second layer. We conclude that the stability differences stem from the smaller unit cell on the (111) surface, and the ability of water to more easily form stable hexagonal ice-like structures on the hexagonal substrate.

[1]  U. Diebold,et al.  Water agglomerates on Fe3O4(001) , 2018, Proceedings of the National Academy of Sciences.

[2]  J. Paier,et al.  Cooperative Formation of Long-Range Ordering in Water Ad-layers on Fe3 O4 (111) Surfaces. , 2018, Angewandte Chemie.

[3]  A. Michaelides,et al.  What makes a good descriptor for heterogeneous ice nucleation on OH-patterned surfaces , 2017, 1709.03852.

[4]  Ying Jiang,et al.  Perspective: Structure and dynamics of water at surfaces probed by scanning tunneling microscopy and spectroscopy. , 2016, The Journal of chemical physics.

[5]  G. Parkinson.  Iron oxide surfaces , 2016, 1602.06774.

[6]  J. Paier,et al.  Adsorption of Water on the Fe3O4(111) Surface: Structures, Stabilities, and Vibrational Properties Studied by Density Functional Theory , 2016 .

[7]  J. Paier,et al.  Water Interaction with Iron Oxides. , 2015, Angewandte Chemie.

[8]  Yi Cui,et al.  Growth of Fe3O4(001) thin films on Pt(100): Tuning surface termination with an Fe buffer layer , 2015 .

[9]  L. Ghiringhelli,et al.  Formation of Water Chains on CaO(001): What Drives the 1D Growth? , 2015, The journal of physical chemistry letters.

[10]  L. Hammer,et al.  Subsurface cation vacancy stabilization of the magnetite (001) surface , 2014, Science.

[11]  Wentao Li,et al.  Water Dissociation on Magnetite (001) Films , 2013 .

[12]  H. Freund,et al.  Well-ordered transition metal oxide layers in model catalysis--a series of case studies. , 2013, Chemical reviews.

[13]  H. Freund,et al.  Defects and inhomogeneities in Fe3O4(111) thin film growth on Pt(111) , 2012 .

[14]  Ulrike Diebold,et al.  Room temperature water splitting at the surface of magnetite. , 2011, Journal of the American Chemical Society.

[15]  M. Sierka,et al.  Structures of the Ordered Water Monolayer on MgO(001) , 2011 .

[16]  D. F. Ogletree,et al.  Metal- and hydrogen-bonding competition during water adsorption on Pd(111) and Ru(0001). , 2009, Journal of the American Chemical Society.

[17]  M. Scheffler,et al.  Partial dissociation of water on Fe3O4(001): adsorbate induced charge and orbital order. , 2009, Physical review letters.

[18]  O. Dulub,et al.  Local ordering and electronic signatures of submonolayer water on anatase TiO2(101). , 2009, Nature materials.

[19]  M. Scheffler,et al.  A combined DFT/LEED-approach for complex oxide surface structure determination: Fe3O4(0 0 1) , 2008 .

[20]  G. Thornton,et al.  Substrate-termination and H2O-coverage dependent dissociation of H2O on Fe3O4(111) , 2008 .

[21]  A. Michaelides,et al.  Ice nanoclusters at hydrophobic metal surfaces. , 2007, Nature materials.

[22]  D. Marx,et al.  Partial dissociation of water leads to stable superstructures on the surface of zinc oxide. , 2004, Angewandte Chemie.

[23]  Michael A. Henderson,et al.  The Interaction of Water with Solid Surfaces: Fundamental Aspects Revisited , 2002 .

[24]  W. Ranke,et al.  Surface chemistry and catalysis on well-defined epitaxial iron-oxide layers , 2002 .

[25]  H. Over,et al.  Defect structures on epitaxial Fe3O4 (111) films , 1999 .

[26]  W. Weiss,et al.  Fe3O4(111) surface structure determined by LEED crystallography , 1999 .

[27]  W. Weiss,et al.  Metal oxide heteroepitaxy: Stranski-Krastanov growth for iron oxides on Pt(111) , 1999 .

[28]  Patricia A. Thiel,et al.  The interaction of water with solid surfaces: Fundamental aspects , 1987 .

[29]  J. Paier,et al.  Cooperative formation of long-range ordering in water ad-layers on Fe3O4(111) , 2017 .

[30]  U. Diebold,et al.  Probing the Surface Phase Diagram of Fe3O4(001) Towards the Fe Rich Limit: Evidence for Progressive Reduction of the Surface , 2013 .