Adsorbate coordination number

The coordination of Cu + in zeolite rho with other adsorbates than water has also been studied by ESEM methods. Table I summarizes the adsorbate coordination number of water and other adsorbates for Cuz in rho zeolites with various cocations (6,7). 

The preference of CO to adsorb with low coordination relates to the very different coordination preferences of the donating interactions versus backdonating interactions. When doubly occupied orbitals interact with the surface, the bonding and antibonding surface fragment orbitals that are formed can both become occupied and the resulting interaction energy becomes weak or repulsive. The Pauli repulsive interaction between doubly occupied orbitals is approximately proportional to N, the adsorbate coordination number ... 

As we discussed in the previous section, the primary parameter that determines the interaction strength between an adsorbate and a (transition) metal surface is the coordinative unsaturation of the surface metal atoms. The lower the coordination number of a surface atom, the larger the interaction with interacting adsorbates. 

The effects of adsorbate coverage (film thickness) on the Pd 3d5/2 XPS peak positions of the Pd/W(l 1 0), Pd/ Re(0001), and Pd/Mo(l 10) systems were systematically investigated [63]. The peak positions reported for Pd coverage in excess of 1 ML represent a product of electrons emitted from surface and subsurface atoms. For the case of Pd(lOO), theoretical calculation suggest that the Pd 3d5/2 XPS BE of the surface atoms is 0.4 eV lower than that of bulk Pd. A similar difference has been observed experimentally for Ni and Pt surfaces. These shifts in BE are a consequence of variations in the coordination number of the surface atoms compared to bulk atom. If we reference the combined peak of bulk and surface atoms in 40 ML of Pd on W(1 1 0) to that of Pd(l 00) a difference of —0.8 eV is obtained between the Pd 3ds/2 BE of a pseudomorphic monolayer of Pd on W(110) and that of the surface atoms of Pd(l 00). The corresponding shifts... 

Figure 1.4 Proposed steps in the chemisorption of OH on/in Pt, starting with arrays of OH groups over the uppermost metal atom layer, increasing the coordination number of the adsorbed OH by place exchange, and next generating a mixed, metal/oxygen overlayer while further oxidizing to form O atoms. From Conway et al. [1990].

To conduct experiments of this kind it is very convenient to make use of disorder adsorbent provided by a film of amorphous selenium. During deposition under vacuum conditions, the pressure being no higher than lO Torr, the amorphous modification of selenium is being formed [38]. There are two forms of amorphous selenium which differ in coordination numbers and radii of coordination spheres. The first form is... 

As Ti is incorporated in the silicate lattice, the volume of the unit cell expands (consistent with the flexible geometry of the ZSM-5 lattice) (75), but beyond a certain limit, it cannot expand further, and Ti is ejected from the framework, forming extraframework Ti species. Although no theoretical value exists for such a maximum limit in such small crystals, it depends on the type of silicate structure (MFI, beta, MCM, mordenite, Y, etc.) and the extent of defects therein, the latter depending to a limited extent on the preparation procedure. Because of the metastable positions of Ti ions in such locations, they can expand their geometry and coordination number when required (for example, in the presence of adsorbates such as H20, NH3, H2O2, etc.). Such an expansion in coordination number has, indeed, been observed recently (see Section II.B.2). The strain imposed on such 5- and 6-fold coordinated Ti ions by the demand of the framework for four bonds with tetrahedral orientation may possibly account for their remarkable catalytic properties. In fact, the protein moiety in certain metalloproteins imposes such a strain on the active metal center leading to their extraordinary catalytic properties (76). 

The majority of the titanium ions in titanosilicate molecular sieves in the dehydrated state are present in two types of structures, the framework tetrapodal and tripodal structures. The tetrapodal species dominate in TS-1 and Ti-beta, and the tripodals are more prevalent in Ti-MCM-41 and other mesoporous materials. The coordinatively unsaturated Ti ions in these structures exhibit Lewis acidity and strongly adsorb molecules such as H2O, NH3, H2O2, alkenes, etc. On interaction with H2O2, H2 + O2, or alkyl hydroperoxides, the Ti ions expand their coordination number to 5 or 6 and form side-on Ti-peroxo and superoxo complexes which catalyze the many oxidation reactions of NH3 and organic molecules. 

It is noteworthy that surface carbon did not come from those CO molecules responsible for the HT peak but from sites that are able to disproportionate CO and correspond to the LT peak. Because the latter sites are important only on quite small particles, it is tempting to associate them with low coordination number surface metal atoms, the relative concentration of which increases rapidly as the particle size decreases below 2 nm (8). Thus, these atoms may be the sites responsible for the relatively weakly adsorbed state of CO. Results similar to our work were found on other Group VIII metals. In the case of a Ru/Si02 sample, Yamasaki et al. (9) have shown by infrared spectroscopy that the deposition of carbon occurs rapidly by CO disproportionation on the sites for weakly held CO. The disproportionation also occurred on a Rh/Al20 sample with 66% metal exposed so that appreciable concentrations of low coordination atoms are expected (10). 

ESEM results on the interaction of silica-exchanged Cu(II) with a range of adsorbates showed that one or two adsorbate molecules were able to coordinate to the Cu depending on the chemical interaction, polarity and size (7[2). Differences in A, were observed for N- and O-coordinated ligands, but these seem to reflect a change in coordination symmetry and not a difference in adsorbate ligand number. N-coordinated ligands form approximately square planar... 

Metal oxides, 31 78-79, 89, 102, 123, 157-158, 191, 32 199-121 see also Amorphous metal oxides Sulfate-supported metal oxides specific oxides adsorbed oxygen on, 27 196-198 binary, surface acidity, 27 136-138 catalytic etching, 41 390-396 coordination number, 27 136 electrocatalysts, 40 127-128 Fe3(CO)i2 reaction with, 38 311-314 Lewis acid-treated, 37 169-170 multiply-valent metals, electrocatalytic oxidations, 40 154-157 superacids by, 37 201-204 surface acidity, methods for determining, 27 121... 

PtSn-OM and PtSn-OM samples show a more complicated radial distribution function. At least two different scatterer atoms must be present to obtain such a result. Considering the way the catalysts are prepared, a Pt-C and a Pt-Pt shell were used to perform the fits. Before the reduction process, a solvent fraction remains adsorbed on the samples, so the appearance of C near the Pt atoms is natural. Results show that the coordination number for the Pt-Pt shell is smaller in both... 

The adsorption site, i.e. the chemisorption position of the adatoms on (within, below) the substrate surface, thanks to the polarisation dependence of SEXAFS. Often a unique assignment can be derived from the analysis of both polarisation dependent bond lengths and relative coordination numbers. The relative, polarisation dependent, amplitudes of the EXAFS oscillations indicate without ambiguity the chemisorption position if such position is the same for all adsorbed atoms. More than one chemisorption site could be present at a time (surface defect sites or just several of the ideal surface sites). If the relative population of the chemisorption sites is of the same order of magnitude, then the analysis of the data becomes difficult, or just impossible. 

They based this modification on the known adsorbance of OH on glass and on the common occurrence of transition metal mixed water-ammonia complexes with coordination number of 4. Parallel stractural studies of the deposited CdS showed textured growth, supporting a mechanism whereby alternate Cd and S species were involved, in an ion-by-ion process. Such a growth suggests adsorption of a molecular hydroxy-ammine species rather than a cluster. In fact, the mechanism of Ortega-Borges and Lincot also does not differentiate between a hydroxide cluster and molecule. 

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