Characterization supported metals

There is a wealth of information available on CO chemisorption over single-crystal and polycrystalline platinum surfaces under ultrahigh-vacuum conditions research efforts in this area have gained a significant momentum with the advent of various surface analysis techniques (e.g., 2-8). In contrast, CO chemisorption on supported platinum catalysts (e.g., 9, 10, 11) is less well understood, due primarily to the inapplicability of most surface-sensitive techniques and to the difficulties involved in characterizing supported metal surfaces. In particular, the effects of transport resistances on the rates of adsorption and desorption over supported catalysts have rarely been studied. 

EXAFS Results Characterizing Supported Metal Clusters During Catalytic Hydrogenation of Propene Fed in an Equimolar Mixture to a Flow Reactor Operated at Steady State at 25°C and 1 atm (Panjabi, Argo, and Gates, 1999)a... 

In the following we list common methods that have been used to characterize supported metal complexes and show how these techniques can be used to learn more about the surface-metal complex morphologies and chemical properties. 

U V- Vis. Spectroscopic measurements in the ultraviolet and visible range of the electronic spectrum (UV-Vis) can be used to probe electronic transitions in certain metal atoms and ion complexes. The energy of an electronic transition can depend upon the symmetry of the metal ion being different for transitions in a metal complex displaying tetrahedral (Td) symmetry from the same metal showing an octahedral (Oh) symmetry. Thus, it is possible to use UV-Vis spectroscopy to interrogate the symmetry of certain metal ions bound to oxide surfaces. We show here a few examples of the use of UV-Vis spectroscopy to characterized supported metal oxides. 

The chemisorption of some selected probe molecules, typically H2 and CO, is a routine procedure for characterizing supported metal catalysts. In addition to providing basic information about the chemical properties of the dispersed metal phase, these studies are commonly applied to the estimate of metal dispersion data. 

Some of the most thoroughly characterized supported metal complexes are zeolite-supported metal carbonyls. These have been prepared, for example, by the adsorption of Rh(CO)2(acac) on zeolites (e.g., the faujasite zeolite NaY [26] or dealuminated zeolite Y [27]) followed by CO treatment of the resultant material (Fig. 19.3). The IR spectra (not shown, but found in [26, 27]) of the rhodium dicarbonyl represented in Fig. 19.3 are consistent with a square-planar complex (formally Rh(I)) with the Rh atom bonded to two zeolite oxygen atoms. 

The following sections highlight studies employing the computational methods discussed in the previous section to characterize supported metal-oxide systems. It is not intended to be an exhaustive review of the subject, but rather serves to illustrate the strengths and limitations of these methods when applied to supported heterogeneous catalysis. It is broken into three sections corresponding to DFT applied to water-gas-shift (WGS) catalysis (4.3.1), applications of ab initio thermodynamics to assess thermodynamic stability of surfaces (4.3.2), and applications of empirical force-fields (4.3.3). The sections... 

X-ray photoelectron spectra, V3f Alumina-supported metals, multitechnique characterization, 37V-83 Aluminosilicates, Intercalates of, role In heterogeneous catalysis, V72-83 Alumlmin... 

Supported metal carbonyl clusters are alternatively formed from mononuclear metal complexes by surface-mediated synthesis [5,13] examples are [HIr4(CO)ii] formed from Ir(CO)2(acac) on MgO and Rh CCOlie formed from Rh(CO)2(acac) on y-Al203 [5,12,13]. These syntheses are carried out in the presence of gas-phase CO and in the absence of solvents. Synthesis of metal carbonyl clusters on oxide supports apparently often involves hydroxyl groups or water on the support surface analogous chemistry occurs in solution [ 14]. A synthesis from a mononuclear metal complex precursor is usually characterized by a yield less than that attained as a result of simple adsorption of a preformed metal cluster, and consequently the latter precursors are preferred when the goal is a high yield of the cluster on the support an exception is made when the clusters do not fit into the pores of the support (e.g., a zeolite), and a smaller precursor is needed. 

The longer metal-oxygen distances of about 2.6 A observed by EXAFS spectroscopy for these and related supported metal clusters suggest weak interactions between the metal and surface oxygen atoms these EXAFS contributions are not determined with as much confidence as those characterized by the shorter distances, and the interactions are not well understood. 

Much remains to be done to develop the chemistry of organic hgands on supported metal clusters, and substantial progress is to be expected as the samples are well suited to characterization, by IR, NMR, and neutron scattering (F. Li, J. Eckert, and B.C. Gates, unpubhshed results) spectroscopies, as well as density functional theory. 

The foregoing results characterizing structurally simple supported metal clusters can be generalized, at least qualitatively, to provide fundamental understanding that pertains to industrial supported metal catalysts, with their larger, nonuniform particles of metal. 

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