Valence crystal catalysts

Valence, 286 Valence electrons, 269 and ionization energies, 269 Vanadium atomic radius, 399 eleciron configuration, 389 oxidation numbers, 391 pentoxide catalyst, 227 properties, 400, 401 van der Waals forces, 301 elements that form molecular crystals using, 301 and molecular shape, 307 and molecular size, 307 and molecular substances, 306 and number of electrons, 306 van der Waals radius, 354 halogens, 354 Vanillin, 345... 

The valence band structure of very small metal crystallites is expected to differ from that of an infinite crystal for a number of reasons (a) with a ratio of surface to bulk atoms approaching unity (ca. 2 nm diameter), the potential seen by the nearly free valence electrons will be very different from the periodic potential of an infinite crystal (b) surface states, if they exist, would be expected to dominate the electronic density of states (DOS) (c) the electronic DOS of very small metal crystallites on a support surface will be affected by the metal-support interactions. It is essential to determine at what crystallite size (or number of atoms per crystallite) the electronic density of sates begins to depart from that of the infinite crystal, as the material state of the catalyst particle can affect changes in the surface thermodynamics which may control the catalysis and electro-catalysis of heterogeneous reactions as well as the physical properties of the catalyst particle [26]. 

UPS studies of supported catalysts are rare. Griinert and coworkers [45] recently explored the feasibility of characterizing polycrystalline oxides by He-II UPS. A nice touch of their work is that they employed the difference in mean free path of photoelectrons in UPS, V 2p XPS and valence band XPS (below 1 nm, around 1.5 nm, and above 2 nm, respectively) to obtain depth profiles of the different states of vanadium ions in reduced V205 particles [45]. However, the vast majority of UPS studies concern single crystals, for probing the band structure and investigating the molecular orbitals of chemisorbed gases. We discuss examples of each of these applications. 

Trends in the electronic structure of the chalcogenide catalysts have proved to be helpful in the design and understanding of the catalyst clusters. During ORR, the molecular oxygen has been found to react with the cluster as a whole, rather than individual metal atoms.177 The overall number of electrons per cluster unit (NEC) in the valence bond has been shown to have a factor in the activity and stability of the cluster catalysts.177,181 The unsubstituted Chevrel phases have a NEC of 20.177,181 Substituting or intercalating other transition metals into the crystal lattice to make ternary or pseudo-binary Chevrel phases allows for the increase of NEC. It has been found that as the NEC approaches 24, the catalytic activity improves.181 Alonso-Vante compiled the results from his previous studies to show the effect of NEC in... 

From a consideration of the velocity of a number of heterogeneous gas reactions (Eideal and Taylor, Gatalysis in Theory and Practice) a certain number of conclusions may be drawn in respect to the valency of the adsorbate and the number of elementary spaces on the crystal lattice which the adsorbate occupies or adheres to. If we consider a unimolecular reaction to occur catalytically at a surface, e.g. Xg 2X, and that the reactant is but feebly adsorbed by the catalyst, then adopting the previous notation the rate of condensation of the gas on the surface of the catalyst (since the catalyst is almost bare) will be ay,. If the reactant occupies a fraction 6 and each molecule n elementary spaces on the lattice the rate of evaporation of the unchanged product will be vd -. Provided the chemical reaction occur but slowly we obtain (1) ay = vO. ... 

A promoter increases the valence bonds on the catalyst surface by changing the crystal lattice and thereby increasing the active centres. 

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