Semiconductors transition metal oxide surfaces

On semiconductors that are partially ionic and partially covalent, such as transition metal oxides, the surface ion-induced and the surface dangling states may coexist together. 

In a series of transition metal oxide semiconductor powders, photochemical activity in the decarboxylation of oxalic acid was controlled by surface properties and the presence of recombination centers, which in turn depended on the preparation method Similar effects have also been noted in the photodecarboxylation of pyruvic acid and formic acid... 

Non-aqueous synthetic methods have recently been used to assemble mesoporous transition metal oxides and sulfides. This approach may afford greater control over the condensation-polymerization chemistry of precursor species and lead to enhanced surface area materials and well ordered structures [38, 39], For the first time, a rational synthesis of mesostructured metal germanium sulfides from the co-assembly of adamantanoid [Ge4S ()]4 cluster precursors was reported [38], Formamide was used as a solvent to co-assemble surfactant and adamantanoid clusters, while M2+/1+ transition metal ions were used to link the clusters (see Fig. 2.2). This produced exceptionally well-ordered mesostructured metal germanium sulfide materials, which could find application in detoxification of heavy metals, sensing of sulfurous vapors and the formation of semiconductor quantum anti-dot devices. 

The surfaces of metal oxides and their H2 chemisorption characteristics have been far less studied than the surfaces of elemental metals and semiconductors [113,133]. Cation surface states are formed on ideal oxide surfaces at about 2 eV below the bottom ofthe conduction band. The charge of the surface ions is found to be reduced compared with that of the bulk ions and this leads to an enhanced co valency at the surface. The reduction amounts to less than 10 % for oxides of simple metals such as MgO and to 20-30% for transition metal oxides. Cluster and slab calculations reveal that special surface state bands with metallic character can be formed on polar surfaces by charge compensation effects. To what extent the metallic band accounts for special catalytic activity is not yet known [114]. 

The second chemical contribution to the total interaction energy is present if an ionic or a covalent chemical bond between the adsorbed molecule and the surface can be formed. Since covalent bonds also depend on the overlap between the wave functions of the subsystems, their distance dependence is exponential, see Table 1, as is that of the Pauli repulsion. In general, covalent bonds are only possible if at least one of the two partners possesses partially occupied valence orbitals. In contrast to the adsorption at metal or semiconductor surfaces, such a situation is rarely encountered at insulator and in particular at oxide surfaces. In most cases, the ions at the surface of an insulator try to adopt a closed shell electronic structure as they do in the bulk, as for instance the Na+ and Ck ions in NaCl or the Mg + and ions in MgO. Counterexamples are transition metal oxides in which the metal cations possess partially occupied d-shells which might form chemical bonds with the adsorbed molecule. One famous example is the interaction between NO and the NiO(lOO) surface where both the Ni + cations (d configuration with a A2g ground state) and the NO radical ( 11 ground state) have partially filled valence shells (see below). 

In water photooxidation by semiconductor photocatalysis, a sacrificial electron acceptor A, such as Fe or Ag" ions, is usually added to the system to prevent accumulation of any photogenerated electrons. Transition metal oxides, such as RUO2 or Ir02, which are recognised O2 evolution catalysts, are often deposited on the surface of the semiconductor catalyst to improve the efficiency of water oxidation. 

Figure Bl.22.4. Differential IR absorption spectra from a metal-oxide silicon field-effect transistor (MOSFET) as a fiinction of gate voltage (or inversion layer density, n, which is the parameter reported in the figure). Clear peaks are seen in these spectra for the 0-1, 0-2 and 0-3 inter-electric-field subband transitions that develop for charge carriers when confined to a narrow (<100 A) region near the oxide-semiconductor interface. The inset shows a schematic representation of the attenuated total reflection (ATR) arrangement used in these experiments. These data provide an example of the use of ATR IR spectroscopy for the probing of electronic states in semiconductor surfaces [44]-...

To dissociate molecules in an adsorbed layer of oxide, a spillover (photospillover) phenomenon can be used with prior activation of the surface of zinc oxide by particles (clusters) of Pt, Pd, Ni, etc. In the course of adsorption of molecular gases (especially H2, O2) or more complex molecules these particles emit (generate) active particles on the surface of substrate [12], which are capable, as we have already noted, to affect considerably the impurity conductivity even at minor concentrations. Thus, the semiconductor oxide activated by cluster particles of transition metals plays a double role of both activator and analyzer (sensor). The latter conclusion is proved by a large number of papers discussed in detail in review [13]. The papers cited maintain that the particles formed during the process of activation are fairly active as to their influence on the electrical properties of sensors made of semiconductor oxides in the form of thin sintered films. 

Although the role of rare earth ions on the surface of TiC>2 or close to them is important from the point of electron exchange, still more important is the number of f-electrons present in the valence shell of a particular rare earth. As in case of transition metal doped semiconductor catalysts, which produce n-type WO3 semiconductor [133] or p-type NiO semiconductor [134] catalysts and affect the overall kinetics of the reaction, the rare earth ions with just less than half filled (f5 6) shell produce p-type semiconductor catalysts and with slightly more than half filled electronic configuration (f8 10) would act as n-type of semiconductor catalyst. Since the half filled (f7) state is most stable, ions with f5 6 electrons would accept electrons from the surface of TiC>2 and get reduced and rare earth ions with f8-9 electrons would tend to lose electrons to go to stabler electronic configuration of f7. The tendency of rare earths with f1 3 electrons would be to lose electrons and thus behave as n-type of semiconductor catalyst to attain completely vacant f°- shell state [135]. The valence electrons of rare earths are rather embedded deep into their inner shells (n-2), hence not available easily for chemical reactions, but the cavitational energy of ultrasound activates them to participate in the chemical reactions, therefore some of the unknown oxidation states (as Dy+4) may also be seen [136,137]. 

In many catalytic systems, nanoscopic metallic particles are dispersed on ceramic supports and exhibit different stmctures and properties from bulk due to size effect and metal support interaction etc. For very small metal particles, particle size may influence both geometric and electronic structures. For example, gold particles may undergo a metal-semiconductor transition at the size of about 3.5 nm and become active in CO oxidation [10]. Lattice contractions have been observed in metals such as Pt and Pd, when the particle size is smaller than 2-3 nm [11, 12]. Metal support interaction may have drastic effects on the chemisorptive properties of the metal phase [13-15]. Therefore the stmctural features such as particles size and shape, surface stmcture and configuration of metal-substrate interface are of great importance since these features influence the electronic stmctures and hence the catalytic activities. Particle shapes and size distributions of supported metal catalysts were extensively studied by TEM [16-19]. Surface stmctures such as facets and steps were observed by high-resolution surface profile imaging [20-23]. Metal support interaction and other behaviours under various environments were discussed at atomic scale based on the relevant stmctural information accessible by means of TEM [24-29]. 

Since in any catalytic reaction, at least one of the reactants must be chemisorbed, no theory of catalysis can be constructed before the mechanism of chemisorption on the surfaces under investigation is fully understood. In recent years, as a result of the advances in solid-state physics, it became apparent that an important group of adsorbents and catalysts, namely the oxides of the transition metals, were typical semiconductors. This simple idea stimulated both research and speculation in the catalytic field. Its justification is quite simple, at least in qualitative terms. 

Alloys Borates Solid-state Chemistry Carbides Transition Metal Solid-state Chemistry Chalcogenides Solid-state Chemistry Diffraction Methods in Inorganic Chemistry Electronic Structure of Solids Fluorides Solid-state Chemistry Halides Solid-state Chemistry Intercalation Chemistry Ionic Conductors Magnetic Oxides Magnetism of Extended Arrays in Inorganic Solids Nitrides Transition Metal Solid-state Chemistry Noncrystalline Solids Oxide Catalysts in Solid-state Chemistry Oxides Solid-state Chemistry Quasicrystals Semiconductor Interfaces Solids Characterization by Powder Diffraction Solids Computer Modeling Superconductivity Surfaces. 

A large fraction of practical catalysts consists of transition-metal or metal oxide nanoparticles dispersed onto the surface of insulator or semiconductor oxides that function as support materials. For industrial applications, the supports employed are selected on the basis of their surface area (high surface area is usually, but not always, desirable), high thermal and hydrothermal stability, chemical stability, and mechanical strength. 

---