In adsorption on metals

Decrease of the heat of chemisorption with surface coverage. This is a fairly general phenomenon in adsorption on metals and of great importance in relation to catalysis, since catalytic activity tends to depend inversely on the heat of adsorption. 

Another difficulty is met with in adsorption on metallic surfaces. Metals, or rather conducting bodies, are considered as adsorbents with an ideal polarizability. Accepting this view as true does not make it clear whether the metallic properties leading to this ideal polarizability should be assumed to start at the outer peripheries of the surface atoms of the metal or whether we must assume these properties to be found from a plane through the centers of the surface atoms. The choice of the outer boundary of the region of conducting electrons is very important, however, for the assessment of the distance of the adsorbed atom to the metal. 

The justification for suggesting that metal ion configuration may be important with oxides is that several adsorptions on these substances, notably reversible H2 and CO chemisorption, and possibly N2 and hydrocarbon chemisorption, may take place using metal ion electrons. Such bonding may then be akin to that formed in adsorption on metals and cause a common motif of metal and oxide catalysis. 

Electrolyte adsorption on metals is important in electrochemistry [167,168]. One study reports the adsorption of various anions an Ag, Au, Rh, and Ni electrodes using ellipsometry. Adsorbed film thicknesses now also depend on applied potential. 

We consider first some experimental observations. In general, the initial heats of adsorption on metals tend to follow a common pattern, similar for such common adsorbates as hydrogen, nitrogen, ammonia, carbon monoxide, and ethylene. The usual order of decreasing Q values is Ta > W > Cr > Fe > Ni > Rh > Cu > Au a traditional illustration may be found in Refs. 81, 84, and 165. It appears, first, that transition metals are the most active ones in chemisorption and, second, that the activity correlates with the percent of d character in the metallic bond. What appears to be involved is the ability of a metal to use d orbitals in forming an adsorption bond. An old but still illustrative example is shown in Fig. XVIII-17, for the case of ethylene hydrogenation. 

The information on inhibitor adsorption, derived from direct measurements and from inhibitive efficiency measurements, considered in conjunction with general knowledge of adsorption from solution indicates that inhibitor adsorption on metals is influenced by the following main factors. 

The effect of the presence of alkali promoters on ethylene adsorption on single crystal metal surfaces has been studied in the case ofPt (111).74 77 The same effect has been also studied for C6H6 and C4H8 on K-covered Pt(l 11).78,79 As ethylene and other unsaturated hydrocarbon molecules show net n- or o-donor behavior it is expected that alkalis will inhibit their adsorption on metal surfaces. The requirement of two free neighboring Pt atoms for adsorption of ethylene in the di-o state is also expected to allow for geometric (steric) hindrance of ethylene adsorption at high alkali coverages. 

Figure 5.22 reveals the ability of solid state electrochemistry to create new types of adsorption on metal catalyst electrodes. Here oxygen has been supplied not from the gas phase but electrochemically, as 02 via current application for a time, denoted tj, of 1=15 pA at 673 K, i.e. at the same temperature used for gaseous O2 adsorption (Fig. 5.21). Figure 5.23 shows the effect of mixed gaseous-electrochemical adsorption. The Pt surface has been initially exposed to po2 =4x1 O 6 Torr for 1800 s (7.2 kL) followed by electrochemical O2 supply (1=15 pA) for various time periods ti shown on the figure, in order to simulate NEMCA conditions. 

T. Aruga, and Y. Murata, Alkali-metal adsorption on metals, Progress in Surface Science 31, 61-130 (1989). 

As explained in the previous chapters, catalysis is a cycle, which starts with the adsorption of reactants on the surface of the catalyst. Often at least one of the reactants is dissociated, and it is often in the dissociation of a strong bond that the essence of catalytic action lies. Hence we shall focus on the physics and chemistry involved when gases adsorb and dissociate on a surface, in particular on metal surfaces. 

From the theoretical standpoint the above issues are addressed by quantum chemistry. On the basis of calculations of various cluster models [191] the properties of surfaces of solid body are being studied as well as issues dealing with interaction of gas with the surface of adsorbent. However, fairly good results have been obtained in this area only to calculate adsorption on metals. The necessity to account for more complex structure of the adsorption value as well as availability of various functional groups on the surface of adsorbent in case of adsorption on semiconductors geometrically complicates such calculations. 

No "Jilt has so far been assumed that the semiconductor-electrolyte interphase does not contain either ions adsorbed specifically from the electrolyte or electrons corresponding to an additional system of electron levels. These surface states of electrons are formed either through adsorption (the Shockley levels) or through defects in the crystal lattice of the semiconductor (the Tamm levels). In this case—analogously as for specific adsorption on metal electrodes—three capacitors in series cannot be used to characterize the semiconductor-electrolyte interphase system and Eq. (4.5.6) must include a term describing the potential difference for surface states. 

A discussion along this line has been made in regard to the orientation of the hydrogen molecule in the dissociative adsorption on metals 82>. Thus, the interpretation of the function of heterogeneous catalysis on a molecular basis is no longer beyond our reach. The important role of LU MO in the process of polarographic reductions has also been discussed... 

Mn(II) adsorption on metal oxide surfaces. The binding of Mn(II) on y-FeOOH can be understood in a surface coordination chemical framework. The surface groups on a metal oxide are amphoteric and the hydrolysis reactions can be written ... 

Valuable information can be obtained from thermal desorption spectra (TDS) spectra, despite the fact that electrochemists are somewhat cautious about the relevance of ultrahigh vacuum data to the solution situation, and the solid/liquid interface in particular. Their objections arise from the fact that properties of the double layer depend on the interaction of the electrode with ions in the solution. Experiments in which the electrode, after having been in contact with the solution, is evacuated and further investigated under high vacuum conditions, can hardly reflect the real situation at the metal/solution interface. However, the TDS spectra can provide valuable information about the energy of water adsorption on metals and its dependence on the surface structure. At low temperatures of 100 to 200 K, frozen molecules of water are fixed at the metal. This case is quite different from the adsorption at the electrode/solution interface, which usually involves a dynamic equilibrium with molecules in the bulk. 

Table 5-2. The standard chemical free enthalpy, of anion adsorption on metal electrodes in aqueous solution at 25°C. [From Bode, 1972.]...

Pig. 5-27. Contact ion adsorption on metal electrodes in aqueous solution IHP = inner Helmholtz plane OHP = outer Helmholtz plane i,d = adsorbed ion ih = hy-dratedion oM = charge on the metal electrode o i = charge of adsorbed ions o i = charge of excess hydrated ions in solution. [From Bockris-Devanathan-MuUer, 1963.]... 

Ionic contact adsorption on metallic electrodes alters the potential profile across the compact layer at constant electrode potential. If anions are adsorbed on the metal electrode at positive potentials, the adsorption-induced dipole generates a potential across the inner Helmholtz layer (IHL) as illustrated in Fig. 5-29. The electric field in the outer part (OHL) of the compact layer, as a result, becomes dififerent fi om and frequently opposite to that in the inner part (IHL) of the compact layer. 

Fig. 6-3S. Potential energy curves for water adsorption on metal surface in the states of molecules and hydrozjd radicals c = energy r = reaction coordinate solid curve = adsorption as water molecules and as partially dissociated hydroxj4 and hydrogen radicals broken curve = adsorption of completely dissociated oxygen and hydrogen radicals.

Benard, 1983] J. Benard, Adsorption on Metal Surface, Studies in Surface Science and Catalysis 13, p. 150, Elsevier Sd. Pub. Co., Amsterdam, (1983). 

Interest in studying formic acid adsorption on metals by XPS and UPS was stimulated largely by its use as a probe molecule for investigating the role of the electronic factor in heterogeneous catalysis as in the work of Schwab (70), Dowden and Reynolds (71), Eley and Leutic (72), and Fahren-fort et al. (73). The advantages of XPS and UPS are fourfold. 

The possibility of adsorption on a virtual exciton was indicated by E. L. Nagayev (.14) on the simplest example of the adsorption of a one-electron atom. This problem is an example of the many-electron approach in chemisorption theory. Recently, V. L. Bonch-Bruevich and V. B. Glasko (16) have treated adsorption on metal surfaces by the many-electron method. 

For the purposes of this chapter, which focuses on comparisons of isocyanide binding in transition metal complexes and isocyanide adsorption on metal surfaces, we first summarize known modes of isocyanide binding to one, two and three metals in their complexes. In such complexes, detailed structural features of isocyanide attachment to the metals have been established by single-crystal X-ray diffraction studies. On the other hand, modes of isocyanide attachment to metal atoms on metal surfaces are proposed on the basis of comparisons of spectroscopic data for adsorbed isocyanides with comparable data for isocyanides in metal complexes with known modes of isocyanide attachment. 

Table 13.2 Acronyms for techniques used in the study of isocyanide adsorption on metal surfaces.

Chemisorption. Chemisorption involves heats of adsorption which are large as compared to the heat of van der Waal s adsorption. The term chemisorption implies formation of semi-chemical bonds of the adsorbed gas with the solid surface. Chemisorption may be a process involving measurable activation energy—that is, a measurable rate of adsorption and a measurable temperature coefficient of rate of adsorption. As in the case of hydrogen adsorption on metals, chemisorption may have no measurable rate of adsorption, the adsorption being essentially instantaneous. 

A more extensive comparison of DFT-predicted adsorption energies with experimental data for CO adsorption on metal surfaces was made using data from 16 different metal surfaces by Abild-Pedersen and Andersson.13 Unlike the earlier comparison by Hammer et al., this study included information on the uncertainties in experimentally measured adsorption energies by comparing multiple experiments for individual surfaces when possible. These uncertainties were estimated to be on the order of 0.1 eV for most surfaces. In situations where multiple experimental results were available, the mean of the reported experimental results was used for comparison with DFT results. For calculations with the PW91 GGA functional, the mean absolute deviation between the DFT and experimental adsorption... 

Based on the first-principles study of helium adsorption on metals (Zaremba and Kohn, 1977), Esbjerg and Nprskov (1980) made an important observation. Because the He atom is very tight (with a radius about 1 A), the surface electron density of the sample does not vary much within the volume of the He atom. Therefore, the interaction energy should be determined by the electron density of the sample at the location of the He nucleus. A calculation of the interaction of a He atom with a homogeneous electron distribution results in an explicit relation between the He scattering potential V r) and the local electron density p(r). For He atoms with kinetic energy smaller than 0.1 eV, Esbjerg and Nprskov (1980) obtained... 

Turning to metal substrates, in most cases of atomic adsorption on metal surfaces where the adsorption geometry has been determined (cf. Table 6.1), only one adsorption site is involved, i.e., all adatoms have identical surroundings [the exceptions are Ni(l 11)... 

---