Water Agglomerates on Fe3O4(001)

Abstract

Determining the structure of water adsorbed on solid surfaces is a notoriously difficult task, and pushes the limits of experimental and theoretical techniques. Here, we follow the evolution of water agglomerates on Fe3O4(001); a complex mineral surface relevant in both modern technology and the natural environment. Strong OH-H2O bonds drive the formation of partially-dissociated water dimers at low coverage, but a surface reconstruction restricts the density of such species to one per unit cell. The dimers act as an anchor for further water molecules as the coverage increases, leading first to partially-dissociated water trimers, and then to a ring-like, hydrogen-bonded network that covers the entire surface. Unraveling this complexity requires the concerted application of several state-of-the-art methods. Quantitative temperature programmed desorption (TPD) reveals the coverage of stable structures, monochromatic x-ray photoelectron spectroscopy (XPS) shows the extent of partial dissociation, and non-contact Atomic Force Microscopy (AFM) using a CO-functionalized tip provides a direct view of the agglomerate structure. Together, these data provide a stringent test of the minimum energy configurations determined via a van der Waals density functional theory (DFT)-based genetic search.

arXiv comment6 figures, includes SI

References in corpus (13)

• Van der Waals Density Functional for General Geometries
• A Higher-Accuracy van der Waals Density Functional
• Perspective: How good is DFT for water?
• Subsurface Cation Vacancy Stabilization of the Magnetite (001) Surface
• CO adsorption on metal surfaces: a hybrid functional study with plane wave basis set
• Partial dissociation of water on Fe${}_3$O${}_4$(001): adsorbate induced charge and orbital order
• Surface properties of the clean and Au/Pd covered Fe${}_3$O${}_4$(111): a DFT and DFT+$U$ study
• Adsorption of water at the SrO surface of ruthenates
• A Multi-Technique Study of $C{O}_2$ Adsorption on $F{e}_3$$O_4$ Magnetite
• The role of surface defects in the adsorption of methanol on Fe3O4(001)
• Temperature-Dependence of Magnetically-Active Charge Excitations in Magnetite across the Verwey Transition
• Adsorption of CO on the Fe3O4(001) Surface
• Charge order at magnetite Fe3O4(001): surface and Verwey phase transitions

Cited by in corpus (12)

• Unravelling CO adsorption on model single-atom catalysts
• Cluster Catalysis with Lattice Oxygen: Tracing Oxygen Transport from a Magnetite(001) Support onto Small Pt Clusters
• An efficient way to model complex magnetite: assessment of SCC-DFTB against DFT
• Water Structures Reveal Local Hydrophobicity on the In2O3(111) Surface
• Self-limited Growth of an Oxyhydroxide Phase at the Fe3O4(001) Surface in Liquid and Ambient Pressure Water
• Rapid oxygen exchange between hematite and water vapor
• Insight into the interface between Fe${}_3$O${}_4$(001) surface and water overlayers through multiscale molecular dynamics simulations
• Influence of Local Defects on the Dynamics of O-H Bond Breaking and Formation on a Magnetite Surface
• Parametrization of the Fe-Owater cross-interaction for a more accurate Fe3O4/water interface model and its application to a spherical Fe3O4 nanoparticle of realistic size
• Oxygen-Terminated (1x1) Reconstruction of Reduced Magnetite Fe${}_3$O${}_4$(111)
• Mechanism of spin ordering in Fe${}_3$O${}_4$ nanoparticles by surface coating with organic acids
• Interaction of surface cations of cleaved mica with water in vapor and liquid forms