Metal adsorbed species structure

These authors doubt that such interactions can be estimated other than empirically without fairly accurate knowledge of the structure in the interfacial region. Sophisticated scattering, surface force, and force microscopy measurements are contributing to this knowledge however, a complete understanding is still a long way off. Even submonolayer amounts of adsorbed species can affect adhesion as found in metals and oxides [74]. 

The most common ions observed as a result of electron-stimulated desorption are atomic (e. g., H, 0, E ), but molecular ions such as OH", CO", H20, and 02" can also be found in significant quantities after adsorption of H2O, CO, CO2, etc. Substrate metallic ions have never been observed, which means that ESD is not applicable to surface compositional analysis of solid materials. The most important application of ESD in the angularly resolved form ESDIAD is in determining the structure and mode of adsorption of adsorbed species. This is because the ejection of positive ions in ESD is not isotropic. Instead the ions are desorbed along specific directions only, characterized by the orientation of the molecular bonds that are broken by electron excitation. 

Raman spectroscopy has provided information on catalytically active transition metal oxide species (e. g. V, Nb, Cr, Mo, W, and Re) present on the surface of different oxide supports (e.g. alumina, titania, zirconia, niobia, and silica). The structures of the surface metal oxide species were reflected in the terminal M=0 and bridging M-O-M vibrations. The location of the surface metal oxide species on the oxide supports was determined by monitoring the specific surface hydroxyls of the support that were being titrated. The surface coverage of the metal oxide species on the oxide supports could be quantitatively obtained, because at monolayer coverage all the reactive surface hydroxyls were titrated and additional metal oxide resulted in the formation of crystalline metal oxide particles. The nature of surface Lewis and Bronsted acid sites in supported metal oxide catalysts has been determined by adsorbing probe mole-... 

A highly detailed picture of a reaction mechanism evolves in-situ studies. It is now known that the adsorption of molecules from the gas phase can seriously influence the reactivity of adsorbed species at oxide surfaces[24]. In-situ observation of adsorbed molecules on metal-oxide surfaces is a crucial issue in molecular-scale understanding of catalysis. The transport of adsorbed species often controls the rate of surface reactions. In practice the inherent compositional and structural inhomogeneity of oxide surfaces makes the problem of identifying the essential issues for their catalytic performance extremely difficult. In order to reduce the level of complexity, a common approach is to study model catalysts such as single crystal oxide surfaces and epitaxial oxide flat surfaces. 

Changes in electron structure of the surface owing to strong interaction of the valence orbitals of the adsorbed species with the electron gas of the base metal. 

Modern theories of electronic structure at a metal surface, which have proved their accuracy for bare metal surfaces, have now been applied to the calculation of electron density profiles in the presence of adsorbed species or other external sources of potential. The spillover of the negative (electronic) charge density from the positive (ionic) background and the overlap of the former with the electrolyte are the crucial effects. Self-consistent calculations, in which the electronic kinetic energy is correctly taken into account, may have to replace the simpler density-functional treatments which have been used most often. The situation for liquid metals, for which the density profile for the positive (ionic) charge density is required, is not as satisfactory as for solid metals, for which the crystal structure is known. 

Although use of the second harmonic signal from metal surfaces as an indirect probe of chemisorption lacks structural specificity, the utility of the technique is clearly demonstrated by the experiments reported here. The next step in our studies will be to demonstrate how one can directly monitor chemisorption with some degree of molecular specificity via the resonant second harmonic signal from the nonlinear susceptibility of adsorbed species. 

Figure 7 shows SNIFTIRS spectra for isoquinoline molecules adsorbed on mercury. The reference spectrum in each case was obtained at 0.0V vs. a SCE reference electrode at this potential the molecules are believed to be oriented flat on the metal surface. The vibrational frequencies of the band structure (positive values of absorbance) are easily assigned since they are essentially the same as those reported by Wait et al. (22) for pure isoquinoline. The differences in the spectra are that the bands for the adsorbed species exhibit blue shifting of 3-4 cm" relative to those of the neat material, and the relative intensities of the bands for the adsorbed species are markedly changed. 

Vibrational spectroscopy techniques are quite suitable for in situ characterization of catalysts. Especially infrared spectroscopy has been used extensively for characterization of the electrode/solution interphases, adsorbed species and their dependence on the electrode potential.33,34 Raman spectroscopy has been used to a lesser extent in characterizing non-precious metal ORR catalysts, most of the studies being related to characterization of the carbon structures.35 A review of the challenges and applications associated with in situ Raman Spectroscopy at metal electrodes has been provided by Pettinger.36... 

We have recently shown that metal-exchanged zeolites give rise to carbocationic reactions, through the interactions with alkylhalides (metal cation acts as Lewis acid sites, coordinating with the alkylhalide to form a metal-halide species and an alkyl-aluminumsilyl oxonium ion bonded to the zeolite structure, which acts as an adsorbed carbocation (scheme 2). We were able to show that they can catalyze Friedel-Crafts reactions (9) and isobutane/2-butene alkylation (70), with a superior performance than a protic zeolite catalyst. 

We now extend the work to in situ measurements on metal ions adsorbed at the metal oxide/aqueous solution interface. In this report, our previous results are combined with new measurements to yield specific information on the chemical structure of adsorbed species at the solid/aqueous solution interface. Here, we describe the principles of emission Mossbauer spectroscopy, experimental techniques, and some results on divalent Co-57 and pentavalent Sb-119 ions adsorbed at the interface between hematite (a-Fe203) and aqueous solutions. 

Hg UPD on Au(lll) electrodes in the presence of bisulfate anions has been studied by Abruna et al. [27] in order to illustrate the effects of the partial charge, retained by the metal, on the interactions between the adsorbed metal and the anion. In order to obtain structural information on the adsorbed species, the authors have carried out grazing incident X-ray diffraction measurements at several potentials. Three ordered structures were observed depending on the applied potentials, which were adjusted from cyclic voltammograms. At the early stages of Hg UPD, when mercury was still partially charged, an ordered mercurous-sulfate bilayer structure was formed at the electrode... 

A database of molecularly adsorbed species on various surfaces is also included (see Table 4.3). In all cases, the chemisorption energies have been calculated on stepped surfaces using density functional theory (see [56] for details). The metals have been modeled by slabs with at least three close-packed layers. The bcc metals are modeled by the bcc(210) surface and the fee and hep metals have been modeled by the fcc(211) surface. A small discrepancy between the adsorption on the hep metals in the fcc(211) structure is thus expected when the results are compared to the adsorption energies on the correct stepped hep structure instead. When mixing... 

FIG. 9.17 Illustrations of LEED spots and coherent structures formed by adsorbed species, (a) indexing of the LEED spots of W(100) pattern in Figure 9.16a as described in Example 9.7 (b) side view of coherent structures formed by adsorbed (open circles) species on metal surface (c) unit mesh for W(100) with adsorbed oxygen (open circles) (d) unit mesh for W(100) with adsorbed hydrogen (open circles). 

The literature of the vibrational spectra of adsorbed alkynes (acetylene and alkyl-substituted acetylenes) is very much in favor of single-crystal studies, with fewer reported investigations of adsorption on oxide-supported metal catalysts. Fewer studies still have been made of the particulate metals under the more advantageous experimental conditions for spectral interpretation, namely, at low temperatures and on alumina as the support. (The latter has a wide transmittance range down to ca. 1100 cm-1.) A similar number of different single-crystal metal surfaces have been studied for ethyne as for ethene adsorption. We shall review in more detail the low-temperature work which usually leads to HCCH nondissociatively adsorbed surface structures. Only salient features will be discussed for higher temperature ethyne adsorption that often leads to dissociative chemisorption. Many of the latter species are those already identified in Part I from the decomposition of adsorbed ethene. 

But-2-yne has been adsorbed on Pt(lll) and studied by VEELS at 320-500 K (102) and by RAIRS at room temperature (103). It has also been investigated on Ni(lll) by VEELS at 80-300 K (104) and on Cu(lll) by RAIRS at 150 K (105, 106). Three possible structures for the adsorbed species have been considered (I—III). In the first one, I, the triple bond of the parent butyne opens up to give di-cr-bonding to two surface metal atoms in the second, II, an additional 77-bond is formed to a third metal... 

Results obtained using the infrared technique indicate that the chemical identity of the adsorbed olefin is critically dependent upon the availability or otherwise of surface hydrogen. The types of adsorbed species also depend upon the structure of the olefin itself and, at any given temperature, upon the metal. 

Khulbe and Mann [155] have obtained infrared spectra of allene adsorbed on silica-supported cobalt, nickel, palladium, platinum and rhodium. The spectra were similar for all the metals, although variations in band intensity from metal to metal were observed. Addition of hydrogen to the allene-precovered surface resulted in similar spectra to those found for chemisorbed and hydrogenated propene in which the surface species was thought to be an adsorbed prop-1-yl group. The authors concluded that the initial allene spectrum was consistent with the adsorbed species being a 1 2-di-o-bonded allene (structure K)... 

NMR is a widely used and important technique for molecular structure determination as applied to bulk materials, where it competes, often advantageously, with vibrational spectroscopy. However, a lack of sensitivity has limited its application to the study of adsorption on high-area finely divided surfaces. Also, certain metals with bulk magnetic properties—e.g., Fe, Co, and Ni (but not the other group Vlll transition metals)—cannot be studied by the technique as their magnetism causes very broad and weak resonances from adsorbed species. 

In this section we shall consider the results recorded in the literature that pertain to the structures of the adsorbed species. Kinetic or catalytic aspects, as could be relevant to hydrogenation, hydrogenolysis, or metathesis processes, will be treated in Part 11. Spectra of the much-investigated alkenes are discussed in detail in Part I. The spectra of the other principal types of hydrocarbon adsorbates, viz. alkynes, alkanes, cycloalkanes, and aromatics, will be analyzed in Part II. Most results are available for the type-molecules ethene, ethyne, ethane, and benzene as well as for the metals, Pt, Pd, Ni, Rh, and Ru. 

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