Metal adsorbates

At potentials positive to the bulk metal deposition, a metal monolayer-or in some cases a bilayer-of one metal can be electrodeposited on another metal surface this phenomenon is referred to as underiDotential deposition (upd) in the literature. Many investigations of several different metal adsorbate/substrate systems have been published to date. In general, two different classes of surface stmetures can be classified (a) simple superstmetures with small packing densities and (b) close-packed (bulklike) or even compressed stmetures, which are observed for deposition of the heavy metal ions Tl, Hg and Pb on Ag, Au, Cu or Pt (see, e.g., [63, 64, 65, 66, 62, 68, 69 and 70]). In case (a), the metal adsorbate is very often stabilized by coadsorbed anions typical representatives of this type are Cu/Au (111) (e.g. [44, 45, 21, 22 and 25]) or Cu/Pt(l 11) (e.g. [46, 74, 75, and 26 ]) It has to be mentioned that the two dimensional ordering of the Cu adatoms is significantly affected by the presence of coadsorbed anions, for example, for the upd of Cu on Au(l 11), the onset of underiDotential deposition shifts to more positive potentials from 80"to Br and CE [72]. 

On the other hand, Pritchard, more recently, has found that on the (111) plane of both silver and copper, the value of u (Xe) is close to 17-0 A (17-7 for Ag, 16-9 A for Cu) and this corresponds to the spacings in solid xenon rather than in the metal adsorbents. ... 

The analysis of low-melting alloys such as Wood s metal is greatly simplified by complexometric titration, and tedious gravimetric separations are avoided. The alloy is treated with concentrated nitric acid, evaporated to a small volume, and after dilution the precipitated tin(IV) oxide is filtered off heavy metals adsorbed by the precipitate are removed by washing with a known volume of standard EDTA solution previously made slightly alkaline with aqueous... 

We have also carried out preliminary experiments in which we have detected the laser desorption of ethylene, cyanogen, methanol, and benzene from the Pt(s)[7(111) x (100)] surface. These spectra are shown in Figure 9. In the experiments involving ethylene, cyanogen, and methanol only neutral species are desorbed. In the case of benzene we observe the molecular parent ion in the absence of the electron beam. We believe that this is due to resonance multiphoton ionization of the benzene by the laser after desorption (resonance multiphoton ionization of benzene is very efficient with 249 nm radiation). These spectra are in marked contrast to the results of SIMS experiments which produce a wide variety of complex metal-adsorbate cluster ions. In the case of ethylene, our experiments were performed at 140 K, and under these conditions ethylene is known to be a molecular x-bonded species on the surface. In SIMS under these conditions the predominant species is CH (15)t but in the laser desorption FTMS experiments neutral ethylene is the principal species detected at low laser power. 

In this section, the surface chemistry of non-metals adsorbed as thin layers, films or SAMs on gold surfaces is discussed. Although attachment by a sulfur atom is by far the most predominant binding motif, many other elements may be used to bind to gold. Particular focus is given here to surface binding through atoms other than those already extensively covered in the literature. 

Opinions differ on the nature of the metal-adsorbed anion bond for specific adsorption. In all probability, a covalent bond similar to that formed in salts of the given ion with the cation of the electrode metal is not formed. The behaviour of sulphide ions on an ideal polarized mercury electrode provides evidence for this conclusion. Sulphide ions are adsorbed far more strongly than halide ions. The electrocapillary quantities (interfacial tension, differential capacity) change discontinuously at the potential at which HgS is formed. Thus, the bond of specifically adsorbed sulphide to mercury is different in nature from that in the HgS salt. Some authors have suggested that specific adsorption is a result of partial charge transfer between the adsorbed ions and the electrode. 

Compared to the importance of Fe and Mn oxides as metal adsorbing surfaces, the primary role of layer silicates is as a substrate on which Fe and Mn oxides precipitate and coat. This is especially true in arid... 

The relative importance of the two mechanisms - the non-local electromagnetic (EM) theory and the local charge transfer (CT) theory - remains a source of considerable discussion. It is generally considered that large-scale rough surfaces, e.g. gratings, islands, metallic spheres etc., favour the EM theory. In contrast, the CT mechanism requires chemisorption of the adsorbate at special atomic scale (e.g. adatom) sites on the metal surface, resulting in a metal/adsorbate CT complex. In addition, considerably enhanced Raman spectra have been obtained from surfaces prepared in such a way as to deliberately exclude one or the other mechanism. 

Flemming CA, Ferris FG, Beveridge TJ, Bailey GW (1990) Remobilization of toxic heavy metals adsorbed to bacterial wall-clay composites. Appl Environ Microbiol 56 3191-3203... 

The two examples discussed here arc typical in the sense that metal adsorbates with atoms that are smaller than those of the substrate tend to form commensurate layers, while adsorbates with bigger atoms tend to form incommensurate monolayers [7]. 

The other mechanism involves atomic-size roughness (i.e., single adatoms or small adatom clusters), and is caused by electronic transitions between the metal and the adsorbate. One of the possible mechanisms, photoassisted metal to adsorbate charge transfer, is illustrated in Fig. 15.4. It depends on the presence of a vacant, broadened adsorbate orbital above the Fermi level of the metal (cf. Chapter 3). In this process the incident photon of frequency cjq excites an electron in the metal, which subsequently undergoes a virtual transition to the adsorbate orbital, where it excites a molecular vibration of frequency lj. When the electron returns to the Fermi level of the metal, a photon of frequency (u>o — us) is emitted. The presence of the metal adatoms enhances the metal-adsorbate interaction, and hence increases the cross... 

The M-X or metal-adsorbate region (around 200-450 cm"1), where the metal-carbon, metal- oxygen and metal-nitrogen stretch frequencies in the spectra of adsorbed species are observed. 

Microscopic Subreactions and Macroscopic Proton Coefficients. The macroscopic proton coefficient may be used as a semi-empirical modeling variable when calibrated against major system parameters. However, x has also been used to evaluate the fundamental nature of metal/adsorbent interactions (e.g., 5). In this section, macroscopic proton coefficients (Xj and v) calculated from adsorption data are compared with the microscopic subreactions of the Triple-Layer Model ( 1 ) and their inter-relationships are discussed. 

With XPS it is possible to obtain good analytical information on the amount of metal adsorbed and, in favourable cases, to identify the chemical form of that metal. Oxidation states are readily determined and it can be shown, for example, that adsorption of Co(II) on manganese oxides results in oxidation to Co(III) (38,39), whereas adsorption of Co(II) on zirconia and alumina leads to the formation of cobalt(II) hydroxide (40). With Y-type zeolites hexaaquacobalt(II) is adsorbed as Co(II), and cobalt(III) hexaammlne is adsorbed as Co(III). The XPS spectrum of Co(II) adsorbed on chlorite was consistent with the presence of the hexaaquacobalt(II) ion for pH 3-7 and indicated that no cobalt(II) hydroxide was present (41). With kaollnlte and llllte, Co is adsorbed as Co(II) over the pH range 3-10 (39,42), it being bound as the aqua ion below pH 6 and as the hydroxide above pH 8. Measurements involving Pb have... 

Fortunately, ground waters dissolve and transport metals from mineral deposits at depth to the surface, where the metals adsorb onto the surfaces of organic matter and Fe- and Mn-oxy-hydroxide particles in the soil. Unfortunately, the adsorption of these ions contributes only a small amount of additional metal to the soil, resulting in marginally anomalous... 

Somewhat smaller < -factors and larger hfs intervals were exhibited by charcoal, zeolite, and a carboxylic acid-type exchange resin, indicating more covalent character in the metal-adsorbent bond. 

---