Surface atom oxidation

Figure 8. Schematic description of photo-electron emission and surface atom oxidation in silver particles carrying adsorbed CN" ions. The shift of the Fermi level in the particles is also indicated. The adsorbed CN" ion acts as a trap of the positive hole.

XPS X-ray photoelectron spectroscopy [131-137] Monoenergetic x-rays eject electrons from various atomic levels the electron energy spectrum is measured Surface composition, oxidation state... 

In this present study, we basically showed dependence of the number of reduced cobalt metal surface atoms on dispersion of cobalt oxides along with the presence of rutile phase in titania. Both XRD and SEM/EDX results (not shown) revealed good distribution of cobalt oxides over the titania support. However, it can not differentiate all samples containing various ratios of rutile/anatase phase. Thus, in order to determine the dispersion of cobalt oxide species on titania, a more powerful technique such as TEM was applied with all samples. The TEM micrographs for all samples are shown in Figure 1. The dark spots represented cobalt oxides species present after calcination of samples dispersing on titania consisting various... 

The present research showed a dependence of various ratios of rutile anatase in titania as a catalyst support for Co/Ti02 on characteristics, especially the reduction behaviors of this catalyst. The study revealed that the presence of 19% rutile phase in titania for CoATi02 (C0/RI9) exhibited the highest number of reduced Co metal surface atoms which is related the number of active sites present. It appeared that the increase in the number of active sites was due to two reasons i) the presence of ratile phase in titania can fadlitrate the reduction process of cobalt oxide species into reduced cobalt metal, and ii) the presence of rutile phase resulted in a larger number of reduced cobalt metal surface atoms. No phase transformation of the supports further occurred during calcination of catalyst samples. However, if the ratios of rutile anatase were over 19%, the number of active sites dramatically decreased. 

In Chapter 1 we emphasized that the properties of a heterogeneous catalyst surface are determined by its composition and structure on the atomic scale. Hence, from a fundamental point of view, the ultimate goal of catalyst characterization should be to examine the surface atom by atom under the reaction conditions under which the catalyst operates, i.e. in situ. However, a catalyst often consists of small particles of metal, oxide, or sulfide on a support material. Chemical promoters may have been added to the catalyst to optimize its activity and/or selectivity, and structural promoters may have been incorporated to improve the mechanical properties and stabilize the particles against sintering. As a result, a heterogeneous catalyst can be quite complex. Moreover, the state of the catalytic surface generally depends on the conditions under which it is used. 

Figure 4.28 shows an example where STM recognizes the individual metal atoms in an alloy, thus revealing highly important structural information on the atomic level. The technique does not require a vacuum, and can in principle be applied under in situ conditions (even in liquids). Unfortunately, STM only works on well-defined, planar, and conducting surfaces such as metals and semiconductors, and not on oxide-supported catalysts. For the latter surfaces, atomic force microscopy offers better perspectives. 

Catalytic oxidations on the surface of oxidic materials usually proceed according to the Mars-Van Krevelen mechanism [P. Mars and D.W. van Krevelen, Chem. Eng. Sci. 3 (1954) 41], as illustrated in Fig. 9.17 for the case of CO oxidation. Instead of a surface reaction between CO and an adsorbed O atom, CO2 is formed by reaction between adsorbed CO and an O atom from the metal oxide lattice. The vacancy formed is filled in a separate reaction step, involving O2 activation, often on defect sites. 

In ecent years the utility of extended X-ray absorption fine structure UXAFS) as a probe for the study of catalysts has been clearly demonstrated (1-17). Measurements of EXAFS are particularly valuable for very highly dispersed catalysts. Supported metal systems, in which small metal clusters or crystallites are commonly dispersed on a refractory oxide such as alumina or silica, are good examples of such catalysts. The ratio of surface atoms to total atoms in the metal clusters is generally high and may even approach unity in some cases. 

The STEM Is Ideally suited for the characterization of these materials, because one Is normally measuring high atomic number elements In low atomic number metal oxide matrices, thus facilitating favorable contrast effects for observation of dispersed metal crystallites due to diffraction and elastic scattering of electrons as a function of Z number. The ability to observe and measure areas 2 nm In size In real time makes analysis of many metal particles relatively rapid and convenient. As with all techniques, limitations are encountered. Information such as metal surface areas, oxidation states of elements, chemical reactivity, etc., are often desired. Consequently, additional Input from other characterization techniques should be sought to complement the STEM data. 

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. 

In any case, it is interesting to note that catalytic efficacy has been observed with nano- or mesoporous gold sponges [99-101, 145] suggesting that neither a discrete particle nor an oxide support is actually a fundamental requirement for catalysis. An alternative mechanism invokes the nanoscale structural effect noted in Section 7.2.2, and proposes that the catalytic effect of nanoscale gold structures is simply due to the presence of a large proportion of lowly-coordinated surface atoms, which would have their own, local electronic configurations suitable for the reaction to be catalyzed [34, 49,146] A recent and readily available study by Hvolbaek et al. [4] summarizes the support for this alternate view. 

Figure 7.14 Current density for formic acid oxidation as a function of the fraction of Pt surface atoms blocked by adatoms on two different electrodes (a) Bi/Pt(lll) (b) Sb/Pt(100). (Reprinted with permission from Leiva et al. [1997].)...

Figure 8.8 Series of iniiared spectra during (a) CO2 production and (b) progressive oxidation of COaj[ on Pt3Sn(l 11) in 0.5 M H2SO4 saturated with CO each spectrum was accumulated ftom 50 interferometers at the potential indicated, (c, d) LEED pattern and schematic representation of the p(4 X 4) structure observed on PtsSnflll) after exposing the surface to O2 and electrolyte. The gray dicles are Pt surface atoms, the black circles are Sn atoms covered with OH, and the dotted circles are Sn atoms that are chemically different from Sn atoms modified with OH. (Reprinted with permission from Stamenkovic et al. [2003]. Copyright 1999. The American Chemical Society.)...

Figure 9.6 Visual representation of the platinum oxide growth mechanism, (a) Interaction of H2O molecules with the Pt electrode occurring in the 0.27 V < < 0.85 V range, (b) Discharge of 5 ML of H2O molecules and formation of 5 ML of chemisorbed oxygen (Ochem)- (c) Discharge of the second ML of H2O molecules the process is accompanied by the development of repulsive interactions between (Pt-Pt) -Ofi m surface species that stimulate an interfacial place exchange of Ochem and Pt surface atoms, (d) Quasi-3D surface PtO lattice, comprising Pt and moieties, that forms through the place-exchange process. (Reproduced with permission...

In the anodic scan, the oxidation of the H adlayer formed below 0.1 V and the re-formation of OHad/Oad (both in peak A) are shifted to markedly higher potentials compared with the Oad/OHad removal and Hupd formation (peak A ) in the cathodic scan (Fig. 14.2b). Furthermore, it overlaps with the peak B (OHad oxidation) observed for a cathodic scan limit of 0.1 V. At low scan rates, peak A starts at 0.1-0.15 V and reaches up to 0.48 V. Hence, compared with a scan with a cathodic limit of > 0.1 V, the equilibration of the Oad/OHad adlayer is shifted from 0.28 to 0.48 V. The charge in peak A integrated in the range 0.1-0.48 V corresponds to 1.5 e per surface atom, which is equal to the sum of the charges in peaks B and A in the negative-going scan. 

The influence of Pt modihcations on the electrochemical and electrocatalytic properties of Ru(OOOl) electrodes has been investigated on structurally well-defined bimetallic PtRu surfaces. Two types of brmetalhc surfaces were considered Ru(OOOl) electrodes covered by monolayer Pt islands and monolayer PtRu/Ru(0001) surface alloys with a highly dispersed and almost random distribution of the respective surface atoms, with different Pt surface contents for both types of structures. The morphology of these surfaces differs significantly from that of brmetaUic PtRu surfaces prepared by electrochemical deposition of Pt on Ru(0001), where Pt predominantly exists in small multilayer islands. The electrochemical and electrocatal5d ic measurements, base CVs, and CO bulk oxidation under continuous electrolyte flow, led to the following conclusions ... 

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