Chemisorption level

We have presented the chemisorption results relative to the total amount of rhodium present, that is as O/Rh values. The results demonstrate that, just as for H2 chemisorption, the O2 chemisorption is dependent on time. In the first few hours there is a more or less linear relationship with In t, thereafter the chemisorption levels off. The O2 chemisorption is strongly dependent on the pretreatment too, increasing reduction-evacuation temperature leads to increasing O2 chemisorption (Figure 3 curves A to D). On the other hand the slope of the curves is not much dependent on reduction temperature. 

An electric field can be applied to an insulator with no electrode present through electrostatic charging (sometimes called xerographic charging) [42]. The process involves the generation of ions in the vicinity of a metal point or fine wire by the field emission of electrons from (or to) the metal and the subsequent (or prior) capture (or release) of the electrons by gas atoms. The ions are then drifted to the specimen surface in an applied field and, under certain circumstances, the ions remain stable on the surface to generate an electric field between that surface and the back surface that has been held at ground potential. For this process to take place the interaction between the ions and solid surface must create an electronic level (the so-called chemisorption level of the ion on the insulator surface) that lies well within the band gap of the... 

Vibrational energy states are too well separated to contribute much to the entropy or the energy of small molecules at ordinary temperatures, but for higher temperatures this may not be so, and both internal entropy and energy changes may occur due to changes in vibrational levels on adsoiption. From a somewhat different point of view, it is clear that even in physical adsorption, adsorbate molecules should be polarized on the surface (see Section VI-8), and in chemisorption more drastic perturbations should occur. Thus internal bond energies of adsorbed molecules may be affected. 

The plan of this chapter is as follows. We discuss chemisorption as a distinct topic, first from the molecular and then from the phenomenological points of view. Heterogeneous catalysis is then taken up, but now first from the phenomenological (and technologically important) viewpoint and then in terms of current knowledge about surface structures at the molecular level. Section XVIII-9F takes note of the current interest in photodriven surface processes. 

Ultraviolet photoelectron spectroscopy (UPS) results have provided detailed infomiation about CO adsorption on many surfaces. Figure A3.10.24 shows UPS results for CO adsorption on Pd(l 10) [58] that are representative of molecular CO adsorption on platinum surfaces. The difference result in (c) between the clean surface and the CO-covered surface shows a strong negative feature just below the Femii level ( p), and two positive features at 8 and 11 eV below E. The negative feature is due to suppression of emission from the metal d states as a result of an anti-resonance phenomenon. The positive features can be attributed to the 4a molecular orbital of CO and the overlap of tire 5a and 1 k molecular orbitals. The observation of features due to CO molecular orbitals clearly indicates that CO molecularly adsorbs. The overlap of the 5a and 1 ti levels is caused by a stabilization of the 5 a molecular orbital as a consequence of fomiing the surface-CO chemisorption bond. 

Anodic polarization also may occur. Typically, this begins with the formation of a thin, impervious oxide film, chemisorbed at the anode (as on the surface of stainless steels). However, for most metals used in boiler plant systems this chemisorption process must be aided by anodic corrosion inhibitors to reduce corrosion rates to tolerable levels. An example is the application of nitrite-based inhibitors, widely used in HW heating systems. 

As discussed already in Chapter 2 the work function, , of a solid surface is one of the most important parameters dictating its chemisorptive and catalytic properties. The work function, (eV/atom) of a surface is the minimum energy which an electron must have to escape from the surface when the surface is electrically neutral. More precisely is defined as the energy to bring an electron from the Fermi level, EF, of the solid at a distance of a few pm outside of the surface under consideration so that image charge interactions are negligible. 

Figure 6.14d shows the electron donation interaction (electrons are transferred from the initially fully occupied 5a molecular orbitals to the Fermi level of the metal, thus this is an electron donation interaction). Blyholder was first to discuss that CO chemisorption on transition metal involves both donation and backdonation of electrons.4 We now know both experimentally7 and theoretically96,98 that the electron backdonation mechanism is usually predominant, so that CO behaves on most transition metal surfaces as an overall electron acceptor. 

O showed a profound difference in CO2 formation rate [M.J.P. Hopstaken and J.W. Niemantsverdriet, J. Chem. Phys. 113 (2000) 5457]. Hence, care should be taken to interpret apparent structure sensitivity found under normal operating conditions of high pressure and coverage in terms of the intrinsic reactivity of sites. From the theory of chemisorption and reaction discussed in Chapter 6 it is hard to imagine how the concept of structure insensitivity can be maintained on the level of individual sites on surfaces, as atoms in different geometries always possess different bonding characteristics. 

Figure 2 displays a qualitative correlation between the increase or decrease in CO desorption temperature and relative shifts in surface core-level binding energies (Pd(3d5/2), Ni(2p3/2), or Cu(2p3/2) all measured before adsorbing CO) [66]. In general, a reduction in BE of a core level is accompanied by an enhancement in the strength of the bond between CO and the supported metal monolayer. Likewise, an opposite relationship is observed for an increase in core-level BE. The correlation observed in Figure 2 can be explained in terms of a model based on initial-state effects . The chemisorption bond on metal is dominated by the electron density of the occupied metal orbital to the lowest unoccupied 27t -orbital of CO. A shift towards lower BE decreases the separation of E2 t-Evb thus the back donation increases and vice versa. 

It is of tremendous practical importance that at many metal surfaces chemisorption of a large variety of molecules can occur. This can easily be explained from a discussion on a molecular level as follows. At the surface of a crystal the co-ordination number of the metal atoms is lower than in the bulk of the crystal. Fig. 3.4 illustrates this for Ni. In the bulk the coordination number of all Ni atoms is 12, whereas on the three faces in Fig. 3.4 these numbers are only 8, 7 and 9 for the (100), (110) and (111) surfaces, respectively. So-called free valences exist at the surface. The numbers between brackets are the Miller indices of the surfaces. 

Shek ML, Stefan PM, Binns C, Lindau I, Spicer WE. 1982. Chemisorption-induced Pt 4/ surface core level shifts. Surf Sci 115 L81-L85. 

Thus, the major conclusions of tiie early studies by Volkenshtein and his colleagues applicable to the theory of the method of semiconductor gas sensors are the following a) chemisorption of particles on a semiconductor surface can be accompanied by a charge transfer between adsorption-induced surface levels and volume bands of adsorbent and b) only a certain fraction of absorbed particles is charged, the fraction being dependent on adsorbate and adsorbent. 

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