Chemisorption, anionic cationic

At the Hg electrode/electrolyte-solution interface, the electrical and structural situation is particularly complex (Fig. Id) and can be thought of as the result of combining the electrical anisotropy of the metal interface with that of a dipolar liquid, together with the distribution of dissolved cations and anions that arises, depending on the net charge, q, on the metal, plus any specific chemisorption affinity cations, or especially anions, may have for the metal surface. 

Whenever the concentration of a species at the interface is greater than can be accounted for by electrostatic interactions, we speak of specific adsorption. It is usually caused by chemical interactions between the adsorbate and the electrode, and is then denoted as chemisorption. In some cases adsorption is caused by weaker interactions such as van der Waals forces we then speak of physisorption. Of course, the solvent is always present at the interface so the interaction of a species with the electrode has to be greater than that of the solvent if it is to be adsorbed on the electrode surface. Adsorption involves a partial desolvation. Cations tend to have a firmer solvation sheath than anions, and are therefore less likely to be adsorbed. 

Both cationic adsorption and anionic adsorption belong to what is called ionic adsorption. Covalent adsorption is due to the localized covalent bonding, and metallic adsorption is due to the delocalized covalent bonding. The distinction among these three modes of chemisorption, however, is not so definite that the transition from the covalent through the metallic to the ionic adsorption may not be discontinuous, but rather continuous, in the same way as the transition of the three-dimensional solid compounds between the covalent, metallic, and ionic bonding. 

Such anion adsorption can be prevented by chemisorbing a mono-layer of a strongly adherent thiol molecule to the Au surfaces [97,98]. 1-Propanethiol (PT) was used here because the gold nanotubules can still be wetted with water after chemisorption of the PT monolayer [97].t The Em versus applied potential curves for an untreated and PT-treated gold nanotubule membrane, with KBr solutions present on either side of the membrane, are shown in Fig. 13. The untreated membrane shows only cation permselectivity, but the permselectivity of the PT-treated membrane can be switched, exactly as was the case with the nonadsorbing electrolyte (Fig. 12). 

With the oxide semiconductors, anionic chemisorption would take place over the metal cations, and the interaction problem would be between the orbitals on the foreign atom and the cation band (the 3d band in CU2O, for example). The discussion in this section is relevant if this is the highest filled band. 

With the oxide semiconductors, cationic chemisorption should occur over the lattice anions, and we would expect therefore to have an interaction problem involving the anion bands as well as the cation band. This makes the whole problem much more complicated and because the cation-anion band model is not adequate for the transition metal oxides, we shall not discuss this problem here. 

With the semiconducting oxides, we expect anionic chemisorption to occur over the lattice cations, and our simple molecular orbital theory will be adequate if the conduction band is associated mainly with the cation lattice. This is certainly the case with AI2O3, where there is direct evidence in the soft X-ray emission spectra that the highest filled band is the oxygen 2p band 16). 

On the homopolar line between the A(P and the C(P regions, for example, the usual anionic chemisorption of the last section and the unusual cationic chemisorption of this section coalesce, and a homopolar bond is formed between the foreign atom and the lattice. One electron is lost from an impurity level for each foreign atom adsorbed, and this homopolar chemisorption is depletive. 

The crystal structure of a-Cr203 is made up by a hexagonal close-packed lattice of oxide ions (sequence ABAB ) Two-thirds of the octahedral sites are occupied by Cr3+ ions. Possible idealized surface structures, based on the (001), (100), and (101) planes and the creation of surface sites in the form of coordi-natively unsaturated cations and anions on dehydroxylation of the surface, have been discussed by Burwell et al. (21) and by Stone (144). The (001) face is the most likely crystal plane to predominate in the external surface of well-crystallized a-Cr203 (145). A possible surface model that maintains the overall as well as the local electrical neutrality, as proposed by Zecchina et al. (145) for the dehydroxylated (001) face, is shown in Fig. 2a. It can clearly be seen that equal numbers of four- and five-coordinate Cr3+ ions are to be expected on this idealized surface. Dissociative chemisorption of water would lead to the formation of surface OH groups, as shown in Fig. 2b, for a partially hydroxylated model surface. In fact, on adsorption of D20, Zecchina et al. (145) observed OD-stretching fundamental bands at 2700 and 2675 cm-1, which were narrow and isolated. As evidenced by the appearance of a H20 bending band at 1590... 

Much of our effort involves studies of the chemical behavior of dusters not only as a function of size, but also as a function of metal type, charge state (neutral, cationic or anionic), and reagent molecule. There are two different operating conditions for which we probe the chemisorption of molecules onto clusters as a function of duster size. The first is such that the rate of reaction is kinetically controlled. Here we obtain information about the rate at which the first reagent molecule chemisorbs onto the otherwise bare cluster. In the second case, chemisorption studies are carried out under near steady-state conditions. In this instance we attempt to determine how many molecules a particular size cluster can bind, i.e. the degree of saturation. 

Since the surfaces of metal oxides contain both negatively charged anions and positively charged cations — often with more than one cation valence state present —many avenues of adsorption are available. The various chemisorption and physisorption possibilities on metal oxides are discussed at length in Ref. 1 they will only be briefly summarized here. 

The presence of solution can dramatically affect dissociative chemisorption. In the vapor phase, most metal-catalyzed reactions are homolyticlike, whereby the intermediates that form are stabilized by interactions with the surface. Protic solvents, on the other hand, can more effectively stabilize charge-separated states and therefore aid in heterolytic activation routes. Heterolytic paths can lead to the formation of surface anions and cations that migrate into solution. This is directly relevant to methanol oxidation over PtRu in the methanol fuel cell. The metal-catalyzed route in the vapor phase would involve the dissociation of methanol into methoxy or hydroxy methyl and hydrogen surface intermediates. Subsequent dehydrogenation eventually leads to formation of CO and hydrogen. In the presence of an aqueous media, however, methanol will more likely decompose heterolytically into hydroxy methyl (—1) and intermediates. 

Removal of lattice oxygen from the surface of nickel oxide in vcumo at 250° or incorporation of gallium ions at the same temperature [Eq. (14)] causes the reduction of surface nickel ions into metal atoms. Nucleation of nickel crystallites leaves cationic vacancies in the surface layer of the oxide lattice. The existence of these metal crystallites was demonstrated by magnetic susceptibility measurements (33). Cationic vacancies should thus exist on the surface of all samples prepared in vacuo at 250°. However, since incorporation of lithium ions at 250° creates anionic vacancies, the probability of formation of vacancy pairs (anion and cation) increases and consequently, the number of free cationic vacancies should be low on the surface of lithiated nickel oxides. Carbon monoxide is liable to be adsorbed at room temperature on cationic vacancies and the differences in the chemisorption of this gas are related to the different number of isolated cationic vacancies on the surface of the different samples. 

Cations and anions that adsorb by forming short directional bonds with the surface cannot be considered to be indifferent in character. These ions actually alter the surface charge by the very process of adsorption, and their bonding is classified as chemical adsorption (or chemisorption) in this text. Examples of chemisorption include copper and phosphate adsorption on iron oxides ... 

As with metal cations, anion chemisorption occurs on soil minerals that possess surface hydroxyl groups. The most important minerals in this regard are noncrystalline aluminosilicates (allophanes) oxides and hydroxides of Fe, Al, and Mn and layer silicate clays (edge sites only). It is the H2O or valence-unsatisfied OH ligands bound to surface metal ions (usually Fe, Al, or Mn) that are the sites of chemisorption. In general terms, the surface reaction can be written... 

Compared with cation adsorption on minerals, anion adsorption seems more reversible. For example, selenite and borate reversibly adsorb on reactive soil minerals. A sizable fraction of phosphate adsorbed by soils is rapidly converted to a nonlabile form, however, and phosphate desorption is slow. Even so, a labile fraction remains that is capable of rapid exchange with dissolved phosphate. In the case of phosphate, both chemisorption and precipitation may be occurring, with the latter reaction perhaps accounting for much of the nonlabile fraction. 

The direct consequence of ternary complex formation in soils is likely to be that solubilities of numerous anions and trace metal cations are lowered below those expected from either chemisorption or precipitation. 

---