The interaction between water and oxide surfaces plays an important role in many technological applications and environmental processes. However, gaining fundamental understanding of processes at oxide–water interfaces is challenging because of the complexity of the systems. To this end, results of experimental and computational studies utilizing well-defined oxide surfaces help to gain molecular-scale insights into the properties and reactivity of water on oxide surfaces. This is a necessary basis for the understanding of oxide surface chemistry in more complex environments. This review highlights recent advances in the fundamental understanding of oxide–water interaction using surface science experiments. In particular, we will discuss the results on crystalline and well-defined supported thin film oxide samples of the alkaline earth oxides (MgO and CaO), silica (SiO2), and magnetite (Fe3O4). Several aspects of water–oxide interactions such as adsorption modes (molecular versus dissociative), formation of long-range ordered structures, and dissolution processes will be discussed.

We have investigated the adsorption and dissociation of water and its co-adsorption with CO on atomically defined cobalt oxide nanoislands on Pt(111). The CoO islands were prepared under ultrahigh vacuum (UHV) conditions by reactive deposition of Co metal in oxygen atmosphere. The island structure was characterized by scanning tunneling microscopy (STM), showing that the nanoislands consist of a CoO bilayer and are regularly shaped with island edges that are mainly terminated by Co2+ ions. D2O was dosed in UHV onto the CoO islands on Pt(111) after pre-saturation with CO. D2O dissociation was monitored in situ by isothermal and temperature programmed infrared reflection absorption spectroscopy (IRAS). Isotopic exchange experiments were performed with H2O, D2O, and D218O to elucidate the nature of the hydroxyl groups. Three principal types of OD species are identified: (i) isolated OD at the edges of the CoO islands (Co-OeD), (ii) OD groups within larger hydroxylated areas on the CoO islands (Co-OcD), and (iii) isolated OD groups on the CoO terraces (Co-OtD). At 400 K, water adsorbs dissociatively on the CoO islands and forms isolated hydroxyl species (Co-OeD) at the island edges only. At room temperature (300 K), the coverage of hydroxyl groups increases rapidly, in line with the water-assisted hydroxylation reaction suggested previously. Adsorption experiments with D218O suggest that two equivalent groups are formed from one water molecule after dissociation at island edges, leading to the formation of larger hydroxylated areas on the CoO islands (Co-OcD) and, in addition, isolated OD species on the CoO terraces (Co-OtD). While the initial step of D2O dissociation is facile, the formation of larger hydroxylated areas is a slow and irreversible process. At 200 K, the formation of hydroxylated areas is accompanied by the co-adsorption of molecular water. The hydroxyl groups on the CoO islands are shown to interact with the CO preadsorbed on the CoO/Pt(111) model system. In particular, we observe a new CO species, stabilized by OD groups on the CoO islands, which adsorbs much stronger than CO on the OD-free CoO surface.

A principal mode of corrosion in combustion or fuel cell environments is the formation of volatile hydroxides and oxyhydroxides from metal or oxide surfaces at high temperatures. It is important to determine the degree of volatility and accurate thermodynamic properties for these hydroxides. Significant gaseous metal hydroxides/oxyhydroxides are discussed, along with available experimental and theoretical methods of characterizing species and determining their thermodynamic properties.

The configurations associated with the dissociative adsorption of water on a variety of low-coordinated sites of MgO(100) surfaces, including corners, steps, MgO vacancies, and kinks on 〈010〉 steps, have been studied and assigned by combining infrared spectroscopy and ab initio calculations. Three kinds of MgO powders were examined: powders of very high specific surface area prepared by chemical vapor synthesis and well-defined cubic smoke particles obtained by combustion in either 20:80 or 60:40 O2:Ar mixtures, the latter one involving less defects and smaller particles. It appears that an imperative requirement to obtain a precise characterization of the reactive behavior of defects is to keep the samples in ultra–high vacuum conditions and to control the water partial pressure finely.

Surface water can affect the properties of metal oxide nanoparticles. Investigations on several systems revealed that nanoparticles have different thermodynamic properties than their bulk counterparts due to adsorbed water on their surfaces. Some thermodynamically metastable phases of bulk metal oxides become stable when reduced to the nanoscale, partially due to interactions between high energy surfaces and surface water. Water adsorption microcalorimetry and high-temperature oxide melt solution calorimetry, low-temperature specific heat calorimetry, and inelastic neutron scattering are used to understand the interactions of surface water with metal oxide nanoparticles. Computational methods, such as molecular dynamics simulations and density functional theory calculations, have been used to study these interactions. Investigations on titania, cassiterite, and alumina illustrate the insights gained by these measurements. The energetics of water on metal oxide surfaces are different from those of either liquid water or hexagonal ice, and there is substantial variation in water interactions on different metal oxide surfaces.

Ambient water condenses readily on metal oxides, which can lead to water film formation and water-mediated reactions at the oxide surface. Similar to bulk water, thin water films with thicknesses below 10 molecular layers can modify the oxide surface chemical reactivity and stability. However, due to the confinement of mass transport at the oxide surface, these processes do not proceed exactly as they do in bulk liquid water. In this review article, we will present selected examples from our group and others’ that illustrate the rich interaction of MgO and TiO2 nanostructures with thin water films. We will show that these condensed water films can induce significant chemical, structural, and microstructural transformations of metal oxide nanostructures such as dissolution/precipitation, morphological changes, crystallization, and self-assembly in the solid state.

The kinetics of silica polymerization was measured in silicic acid solutions containing a suite of 0.1 M amino acids, 0.1 M citric acid, 0.7 M NaCl, and 0.10 M NaCl (Control). Fitting a modified classical rate model to measurements of induction time (τ) at 20 °C for a series of supersaturated solutions, we estimate the thermodynamic barrier (ΔGc), interfacial free energy (γ), and kinetic barrier (Δagk) for silica nucleation. For 0.10 M NaCl solutions, γControl = 54.9 ± 1.6 mJ/m2 and ΔagkControl = 2.29 × 10−19 J/mol. These values are consistent with previous reports for amorphous and fused silica materials. To facilitate comparisons with the treatments, ΔagkControl is converted to a molar basis and used as a reference datum, such that ΔagkControl = 0.0 J/mol. The effects of salt and organic acids on nucleation rate have thermodynamic and kinetic origins, respectively. Faster nucleation rates measured in 0.7 M NaCl solutions arise from a lower interfacial free energy, such that γ0.7 M NaCl = 51.4 ± 1.7 mJ/m2. Organic acids increase rate through biomolecule-specific reductions in Δagk. Catalytic effects are greatest for lysine (Δagklysine = −1685 ± 315) and citric acid (Δagkcitric = −1690 ± 96 J/mol). Reductions in the kinetic barrier correlate with net positive charge of the amino acids and dissociation of the amine $\left( {{K_{\alpha {\rm{ ‐ N}}{{\rm{H}}_3}^ {\bf{+}} }}} \right)$ group and thus the abundance of the conjugate base. Citric acid, lacking amine groups, promotes the greatest rate enhancement, thus demonstrating the role(s) of additional kinetic factors in promoting nucleation rate. Catalytic activity correlates with multiple physical and chemical properties of the organic acids.

When a metal oxide surface is immersed in aqueous solution, it has the ability to bind, orient, and order interfacial water, affecting both chemical and physical interactions with the surface. Structured interfacial water thus possesses time-averaged, spatially varying polarization charge and potential that are comparable to those arising due to ion accumulation. It is well established that interfacial water structure propagates from the surface into bulk solution. Here, we show that interfacial water structure also propagates laterally, with important consequences. The constant pH molecular dynamics was used to impose a pH difference between opposite faces of a model goethite (α-FeOOH) nanoparticle and quantify water polarization charge on intervening faces. We find that the structure of water on one face is strongly affected by the structure on nearby surfaces, revealing the importance of long-range lateral hydrogen bonding networks with implications for particle aggregation, oriented attachment, and processes such as dissolution and growth.

Cerium oxide nanoparticles (CNPs) are of significant interest to the scientific community due to their widespread applications in a variety of fields. It is proposed that size-dependent variations in the extent of Ce3+ and Ce4+ oxidation states of cerium in CNPs determine the performance of CNPs in application environments. To obtain greater molecular and structural understanding of chemical state transformations previously reported for ceria of ≈3 nm nanoparticles (CNPs) in response to changing ambient conditions, micro-XRD and Raman measurements were carried out for various solution conditions. The particles were observed to undergo a reversible transformation from a defective ceria structure to a non-ceria amorphous oxyhydroxide/peroxide phase in response to the addition of 30% hydrogen peroxide. For CNPs made up of ∼8 nm crystallites, a partial transformation was observed, and no transformation was observed for CNPs made up of ∼40 nm crystallites. This observation of differences in size-dependent transition behavior may help explain the benefits of using smaller CNPs in applications requiring regenerative property.

Pressureless sintering is a simple and traditional processing method for producing dense ceramics by heating at a high temperature. The introduction of water vapor into this atmosphere can decrease the sintering temperature and accelerate grain growth. In this work, we report water vapor-assisted sintering of submicrometer titania (TiO2) powder. Dense TiO2 pellets with a relative density over 99% were obtained in 0.1 MPa of water vapor at a lower temperature than in air. The submicrometer particles (∼0.5 µm) grew to an average size of 181 µm after sintering at 1400 °C in water vapor, whereas the particle size obtained by sintering in air was 51 µm. Furthermore, we verified the incorporation of oxygen from water vapor into TiO2 by using isotopically labeled water (H218O). Water vapor-assisted sintering can potentially lead to the production of single crystal-like ceramics by a pressureless route and without any additives.