The Chemistry of Extended Oxide Surfaces

In Chapters 4 and 5, we demonstrated that local structures and charge distributions have an enormous impact on the equilibrium constants, trajectories, and kinetics of reactions involving soluble oxide precursors. In this chapter, we highlight those features that make reactions on extended oxide surfaces either similar to or dramatically different from the reactions documented in hydrolysis diagrams for each metal cation (see Chapter 5). We first describe oxide surface structures and then discuss how these structures impact both acid–base and ligand-exchange phenomena. In addition to dense oxides, we also introduce some of the chemistry associated with layered materials. Lamellar materials are important from both a fundamental and technological perspective, because water and ions can readily penetrate such structures and provide conditions under which almost every oxygen anion is at an oxide–water interface (see Chapter 10 and Chapter 11). This chapter focuses on oxides containing octahedral cations. The distinctive chemistry of oxides based on tetrahedral cations, including the clay minerals and the zeolites, are the focus of Part Five. The structures of bulk oxides were introduced in Chapter 2. However, for many oxides, the surface structures that interact with aqueous solutions are substantially different from structures found in the bulk. Here, we introduce the basic principles of oxide surfaces that make them chemically active. As a starting point, consider ideal oxide surfaces containing +2 octahedral cations. Pristine oxide surfaces can be created by cleaving perfect crystals in an ultrahigh-vacuum environment. The creation of new surfaces requires an expenditure of energy corresponding to the cohesive energy of the solid, which in turn represents the energy required to break every bond along a given fracture plane. For MgO, the Mg−O bond energy is 380 kJ/mole. Each surface created contains 1.4.1019 oxygen atoms/m2, or 2.4.10−5 moles of bonds. Because two surfaces are created in the fracture event, the initial interfacial energy of each resulting MgO surface is (1/2)(380 kJ/mole)/(2.4_10−5 mole/m2 )=4560 mJ/m2.