Chemisorption characteristics

A typical adsorption process in electrocatalysis is chemisorption, characteristic primarily for solid metal electrodes. The chemisorbed substance is often chemically modified during the adsorption process. Then either the substance itself or some fragment of it is bonded chemically to the electrode. As electrodes mostly have physically heterogeneous surfaces (see Sections 4.3.3 and 5.5.5), the Temkin adsorption isotherm (Eq. 4.3.46) is suitable for characterizing the adsorption. 

The pH-independence of Tdhpz at Pt indicates that the driving force for coordination of the nitrogen heteroatom to the Pt surface is much larger than that for protonation even in molar acid. This behavior is in contrast to that of pyridine, where protonation of the nitrogen heteroatom in molar acid hinders N-coordination to the surface (H). Such a difference in chemisorption characteristics may be related to the fact that the basicity of the nitrogen heteroatom in pyridine (pKb =8.8) is much greater than that of the nitrogens in pyridazine (pKb = 11.8) (23.). ... 

First we study the surface structure and chemisorption characteristics of crystals cut along different crystallographic orientations. Then a well-chosen chemical reaction is studied at low pressure to establish correlations between reactivity and surface structure and composition. Below 10 4 Torr the surface can be monitored continuously during the reaction with various electron spectroscopy techniques. Then the same catalytic reaction is studied at high pressures (1-100 atm) and the pressure dependence of the reaction rate is determined using the same sample over the nine orders of magnitude range. Finally, the rates and product distributions that were determined at... 

The chemisorption of over 25 hydrocarbons has been studied by LEED on four different stepped-crystal faces of platinum (5), the Pt(S)-[9(l 11) x (100)], Pt(S)-[6(l 11) x (100)], Pt(S)-[7(lll) x (310)], and Pt(S)-[4(l 11 x (100)] structures. These surface structures are shown in Fig. 7. The chemisorption of hydrocarbons produces carbonaceous deposits with characteristics that depend on the substrate structure, the type of hydrocarbon chemisorbed, the rate of adsorption, and the surface temperature. Thus, in contrast with the chemisorption behavior on low Miller index surfaces, breaking of C-H and C-C bonds can readily take place at stepped surfaces of platinum even at 300 K and at low adsorbate pressures (10 9-10-6 Torr). Hydrocarbons on the [9(100) x (100)] and [6(111) x (100)] crystal faces form mostly ordered, partially dehydrogenated carbonaceous deposits, while disordered carbonaceous layers are formed on the [7(111) x (310)] surface, which has a high concentration of kinks in the steps. The distinctly different chemisorption characteristics of these stepped-platinum surfaces can be explained by... 

The chemisorption of acetylene, ethylene, benzene, and cyclohexane were also studied on the Ir(lll) and stepped Ir[6(111) x (100)] crystal surfaces (30). Chemisorption characteristics of the Ir(lll) and Pt(lll) surface are markedly different. Also, the chemisorption characteristics of the low Miller index Ir(l 11) surface and the stepped Ir[6(l 11) x (100)] surface are markedly different for each of the molecules studied. The hydrocarbon molecules form only poorly ordered surface structures on either the Ir(l 11) or stepped iridium surfaces. Acetylene and ethylene (C2H2 and C2H4) form surface structures that are somewhat better ordered on the stepped iridium than on the low Miller index Ir(l 11) metal surface. The lack of ordering on iridium surfaces as compared to the excellent ordering characteristics of these molecules on... 

If the adsorption energy is of the order of chemical binding energies we talk about chemisorption. Characteristic properties are ... 

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 chemisorption characteristic is the strong interaction between molecules and surfaces. The chemisorption enthalpy (—AHads) is of the order of 10-100 kcal/mol, thus, of the same order of the reaction involved in chemical bindings. 

OCP transients Overall chemisorption characteristics, stability of surface composition, preliminary evaluation of galvanic couples Turk et al. (2013b), Turk et al. (2013a), Lagudu et al. (2013), Rock et al. (2012)... 

Different types of chemisorption sites may be observed, each with a characteristic A value. Several adsorbed states appear to exist for CO chemisorbed on tungsten, as noted. These states of chemisorption probably have to do with different types of chemisorption bonding, maybe involving different types of surface sites. Much of the evidence has come initially from desorption studies, discussed immediately following. 

Equation (6.20) and the semiquantitative trends it conveys, can be rationalized not only on the basis of lateral coadsorbate interactions (section 4.5.9.2) and rigorous quantum mechanical calculations on clusters89 (which have shown that 80% of the repulsive O2 - O interaction is indeed an electrostatic (Stark) through-the-vacuum interaction) but also by considering the band structure of a transition metal (Fig. 6.14) and the changes induced by varying O (or EF) on the chemisorption of a molecule such as CO which exhibits both electron acceptor and electron donor characteristics. This example has been adapted from some rigorous recent quantum mechanical calculations of Koper and van Santen.98... 

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. 

The similarity of the results obtained for finite elusters and the infinite slab allows to eonclude in favour of the validity of the eluster model of adequate size (6 or 8 molybdenum atoms). In addition to the chemisorption of organic molecules on solid surfaces which is generally considered as a localized phenomenon, the interaction between molybdenum oxide and an adsorbate can also be represented by a loeal eomplex formed by a finite eluster and the adsorbed molecule. Indeed, the study of the evolution of the electronic properties as a funetion of the cluster size shows that, for a eluster eontaining 6 or 8 molybdenum atoms, most of the electronic properties converge towards limit values. This eonvergence is sensitive to the direction of the cluster growth. On the other hand, the electronic properties of the (001), (010) and (100) faces are not identieal, the type of surface atoms being different these results allow to predict that the characteristics of the chemisorption step will depend on the particular face on which it takes place. 

Thus, sensor effect deals with the change of various electrophysical characteristics of semiconductor adsorbent when detected particles occur on its surface irrespective of the mechanism of their creation. This happens because the surface chemical compounds obtained as a result of chemisorption are substantially stable and capable on numerous occasions of exchanging charge with the volume bands of adsorbent or directly interact with electrically active defects of a semiconductor, which leads to direct change in concentration of free carriers and, in several cases, the charge state of the surface. 

Hence, BSS recharging substantially hinders the adsorption-induced change in degree of barrier disarrangement of adsorbent and in several cases can bring about small sensitivity of electrophysical characteristics of adsorbent to the adsorption process. We should note that above BSS recharging can be one of reasons of notable effect of adsorbent manufacturing prehistory of and the methods to treat its surface on the value and kinetics of chemisorption response. 

All major characteristics of chemisorption response of electrophysical parameters of semiconductor adsorbents such as sensitivity, selectivity, inertia, reversibility are naturally dependent both on the nature of adsorbent and on chemical activity of absorbate with respect to adsorbent chosen. 

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