Sites coordinatively unsaturated

Recenl work has defined more carefully ihe nature of active sites. Metal surfaces are thought to contain three main types of sites terraces, ledges (or steps) and kinks, which correspond to one, two. and three coordinatively unsaturated sites of organometallic chemistry. These sites display differing activities toward saturation, isomerization, and CKChiingQ 7 J0,68 JO 1.103,104,105). [Pg.29]

CoSx-MoSx/NaY exhibited doublet bands at 1867 and 1807 cm, accompanying a weak shoulder peak at ca. 1880 cm. These signals are apparently assigned to those of NO molecules adsorbed on Co sulfides. No peaks ascribable to e NO adsorption on Mo sulfide sites were detected at all. What is important in Fig.7 is that in CoSx-MoSx/NaY, coordinative unsaturation sites are present only on the Co sites in spite of the coexistence of the same amount of Mo sulfide species in the zeolite cavities. These results clearly support that the Co sites in CoSx-MoSx/NaY play major roles in the HYD and HDS reactions. [Pg.509]

The important feature is the formation of a coordinatively unsaturated site (cus), permitting the reaction to occur in the coordinative sphere of the metal cation. The cus is a metal cationic site that is able to present at least three vacancies permitting, in the DeNOx process, to insert ligands such as NO, CO, H20, and any olefin or CxHyOz species that is able to behave like ligands in its coordinative environment. A cus can be located on kinks, ledges or corners of crystals [16] in such a location, they are unsaturated. This situation is quite comparable to an exchanged cation in a zeolite, as studied by Iizuka and Lundsford [17] or to a transition metal complex in solution, as studied by Hendriksen et al. [18] for NO reduction in the presence of CO. [Pg.147]

In this chapter, we have discussed the application of metal oxides as catalysts. Metal oxides display a wide range of properties, from metallic to semiconductor to insulator. Because of the compositional variability and more localized electronic structures than metals, the presence of defects (such as comers, kinks, steps, and coordinatively unsaturated sites) play a very important role in oxide surface chemistry and hence in catalysis. As described, the catalytic reactions also depend on the surface crystallographic structure. The catalytic properties of the oxide surfaces can be explained in terms of Lewis acidity and basicity. The electronegative oxygen atoms accumulate electrons and act as Lewis bases while the metal cations act as Lewis acids. The important applications of metal oxides as catalysts are in processes such as selective oxidation, hydrogenation, oxidative dehydrogenation, and dehydrochlorination and destructive adsorption of chlorocarbons. [Pg.57]

The fact that surface structure, in particular steps and coordinatively unsaturated sites, has an influence on the state and reactivity of carbon monoxide is entirely in keeping with the empirical correlation (Fig. 6) between heat of adsorption, electron binding energies, and molecular state. Elegant studies by Mason, Somorjai, and their colleagues (32, 33) have established that with Pt(lll) surfaces, dissociation occurs at the step sites only, and once these are filled carbon monoxide is adsorbed molecularly (Fig. 7). The implications of the facile dissociation of carbon monoxide by such metals as iron, molybdenum, and tungsten for the conversion of carbon monoxide into hydrocarbons (the Fischer-Tropsch process) have been emphasized and discussed by a number of people (32,34). [Pg.67]

The pretreatment temperature is an important factor that influences the acidic/ basic properties of solids. For Brpnsted sites, the differential heat is the difference between the enthalpy of dissociation of the acidic hydroxyl and the enthalpy of protonation of the probe molecule. For Lewis sites, the differential heat of adsorption represents the energy associated with the transfer of electron density toward an electron-deficient, coordinatively unsaturated site, and probably an energy term related to the relaxation of the strained surface [147,182]. Increasing the pretreatment temperature modifies the surface acidity of the solids. The influence of the pretreatment temperature, between 300 and 800°C, on the surface acidity of a transition alumina has been studied by ammonia adsorption microcalorimetry [62]. The number and strength of the strong sites, which should be mainly Lewis sites, have been found to increase when the temperature increases. This behavior can be explained by the fact that the Lewis sites are not completely free and that their electron pair attracting capacity can be partially modified by different OH group environments. The different pretreatment temperatures used affected the whole spectrum of adsorption heats... [Pg.227]

Vacancies were later called coordinately unsaturated sites (cus). This is more in line with terminology used in organometallic chemistry. In view of the present understanding of the nature of the active sites, SBMS or Co(Ni)-Mo-S, the following discussion describes mechanisms in terms of catalysis by organometallic complexes. The references available on this topic are too numerous to mention, and the mechanisms are very well understood. A particularly useful reference is the book by Candlin, Taylor, and Thompson (90), although there are many others that can be consulted. [Pg.417]

If a catalytic cycle composed of several elementary processes is promoted on an isolated single site, we could make distinctions about the function of the active sites. For example, some metal complexes which are active for the isomerization reaction of olefins via alkyl intermediates are not effective catalysts for the hydrogenation reaction, and such differences in catalytic ability of the metal complexes is explained by the numbers of coordinatively unsaturated sites which are available for the reactions as described schematically in Scheme 7. [Pg.104]

The high basicity of Mgo is associated with the presence of surface °2 Cus (cus= coordinatively unsaturated site) their concentration depends on thermal pretreatment and it shows a maximum around 700°C [23]. A sample of Mgo catalyst pretreated at 650°C showed only a negligible enhancement of the amount of condensation products suggesting that 02-cug are not responsible for them (however during the condensation reaction water is produced which could saturate 0 cus) Higher basic strength of surface OH group of CaO and SrO [22] should promote the condensation reactions. [Pg.258]

Scheme I. Possible C, hydrocarbon species on metal surfaces. On metal surfaces the M atoms are usually bonded together. These ate alternative to the upper row of structures. They are most likely to occur on /-election-deficient metals to the left of the Iransition-metal periods, or on coordinatively unsaturated sites on metals to the right of these periods.

Topics 1-3 can be addressed by the combined use of electron microscopy [HRTEM and scanning electron microscopy (SEM)] (47) and methods that probe the surfaces at the atomic level (e.g., by analyzing the modifications induced in the vibrational spectra of simple probe molecules adsorbed on the different coordinatively unsaturated sites (22, 23). [Pg.274]

The influence of the pre-treatment temperature on the acidic properties is a very important factor. For Bronsted sites, the differential heat is the difference between the enthalpy of dissociation of the acidic hydroxyl and the enthalpy of protonation of the probe molecule. For Lewis sites, the differential heat of adsorption represents the energy associated with the transfer of electron density towards an electron-deficient, coordinatively unsaturated site, and probably an energy term related to the relaxation of the strained surface [40]. [Pg.404]

This reaction may continue past the first ligand exchange reaction to completion. When the surface of metal oxide also contains coordinately unsaturated sites, such as on the surface of some aluminas, then another reaction is possible between the volatile metal acetylacetonate and the surface ... [Pg.77]

Fig. 40. Probe molecule transformations on coordinatively unsaturated sites (CUS) of M0S2. (a) Isomerization and hydrogenation of diene (b) hydrogenation of toluene (c) hychogenation of pyridine (d) HDN of pyridine [adapted from Hubaut et al. (138) reprinted with permission].

In the field of catalysts characterization the use of small unreactive probe molecules to identify coordinatively unsaturated sites is well established [89]. Not always, however, a direct correlation between the CO vibrational frequency, the strength of the interaction, and the surface electric field exists. Recent DPT cluster calculations [90] have shown that CO adsorbed on step sites gives rise to a relatively strong interaction but to a negligible CO vibrational shift this is due to the inhomogeneity in the electric field above a MgO(lOO) step. This study [90] has permitted the complete attribution of the IR spectrum of CO adsorbed on MgO [81,83,91], Table 2. [Pg.106]

In all of Section V to this point, what has been said with respect to chromia could be transferred with little change to alumina. However, data in the literature suggest that Eq. (3), the reaction which generates surface coordinatively unsaturated sites, is more difficult on... [Pg.15]

Table VI illustrates still another important property of supports vis-a-vis homogeneous carbonyl complexes the ability to inaobilize coordinatively unsaturated sites. It is noteworthy that in solution Fe(C0)3 maintained a slight activity only in the presence of continued irradiation, whereas all measurements on the supported catalysts were made in the dark after photoactivation.

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