Catalyst electronic properties

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... 

We start by considering a schematic representation of a porous metal film deposited on a solid electrolyte, e.g., on Y203-stabilized-Zr02 (Fig. 5.17). The catalyst surface is divided in two distinct parts One part, with a surface area AE is in contact with the electrolyte. The other with a surface area Aq is not in contact with the electrolyte. It constitutes the gas-exposed, i.e., catalytically active film surface area. Catalytic reactions take place on this surface only. In the subsequent discussion we will use the subscripts E (for electrolyte) and G (for gas), respectively, to denote these two distinct parts of the catalyst film surface. Regions E and G are separated by the three-phase-boundaries (tpb) where electrocatalytic reactions take place. Since, as previously discussed, electrocatalytic reactions can also take place to, usually,a minor extent on region E, one may consider the tpb to be part of region E as well. It will become apparent below that the essence of NEMCA is the following One uses electrochemistry (i.e. a slow electrocatalytic reaction) to alter the electronic properties of the metal-solid electrolyte interface E. 

Figure 5.17. Schematic representation of a metal crystallite deposited on YSZ and of the changes induced in its electronic properties upon polarizing the catalyst-solid electrolyte interface and changing the Fermi level (or electrochemical potential of electrons) from an initial value p to a new value p -eri30 31 Reprinted with permission from Elsevier Science.

This chapter follows the organization used in the past. A summary of the electronic properties leads into reports of electrocyclic chemistry. Recent reports of studies of HDS processes and catalysts are then summarized. Thiophene ring substitution reactions, ring-forming reactions, the formation of ring-annelated derivatives, and the use of thiophene molecules as intermediates are then reported. Applications of thiophene and its derivatives in polymers and in other small molecules of interest are highlighted. Finally, the few examples of selenophenes and tellurophenes reported in the past year are noted. 

The catalytic hydroformylation of alkenes has been extensively studied. The selective formation of linear versus branched aldehydes is of capital relevance, and this selectivity is influenced by many factors such as the configuration of the ligands in the metallic catalysts, i.e., its bite angle, flexibility, and electronic properties [152,153]. A series of phosphinous amide ligands have been developed for influencing the direction of approach of the substrate to the active catalyst and, therefore, on the selectivity of the reaction. The use of Rh(I) catalysts bearing the ligands in Scheme 34, that is the phosphinous amides 37 (R ... 

Catalysts with Pd deposited on various supports such as Zr02 or mixed supports such as Al203-Zr02-Ba0 have been used for the elimination of NOx. Their activity in the presence of complex mixtures like CO-NO-O2-C3H5-CO2-H2O is better than that of Pd/Al203. This increase in activity is due not to a modification of the electronic properties of Pd but to a direct participation of the support in the process From the analysis of the experimental results, a biflinctional mechanism is proposed and discussed. 

By single-site catalysts we mean catalysts where the breaking and formation of chemical bonds occurs at isolated active centers whose chemical activity is dominated by the electronic properties of a single atomic species or of a small cluster of atoms that can act in an independent way with respect to others. 

These results suggest that imidazolidin- and imidazol-based skeletons transfer similar amounts of electron density to the metal. The conclusion that changes in the bridge of the NHC skeleton have such a small effect on the electronic properties of the NHC is quite surprising, considering that SIMes- and IMes-based catalysts often show remarkably different catalytic behaviour. It is still unclear if these small changes in the electronic properties of the NHC ligand confer such different catalytic behaviours, or other effects (steric, flexibility, etc.) should be invoked. 

Carbene ligands can replace phosphines dne to similar electronic properties. The development of NHC design concepts featnring different substituents and backbones eventually culminated in the most prominent derivative, the SIMes (SDVtes = A, A -bis[2,4,6-(trimethyl)phenyl]imidazolidin-2-ylidene) ligand that is nsed in the second and later also third generation catalysts (complexes 72, 73, 74b and 74c in Fig. 3.28) [105, 109, 114,116],... 

Interpretation of this observed correlation between a lowered affinity of the metal surface to oxygen and a higher rate of ORR measured at a Pt shell over a Pt-alloy core has also been at the center of recent theoretical work, based primarily on DFT calculations of electronic properties and surface bond strengths for a variety of expected ORR intermediates at metal and metal alloy catalysts. The second part of this chapter contains a discussion of these valuable contributions and of outstanding issues in tying together this recent theoretical work and ORR experimental data. 

Mayrhofer KJJ, Blizanac BB, Arenz M, Stamenkovic VR, Ross PN, Markovic NM. 2005b. The impact of geometric and surface electronic properties of Pt-catalysts on the particle size effect in electrocatalysis. J Phys Chem B 109 14433-14440. 

Supported Co, Ni, Ru, Rh, Pd and Pt as well as Raney Ni and Co catalysts were used for the hydrogenation of dodecanenitrile to amines in stirred SS autoclaves both in cyclohexane and without a solvent. The reaction temperature and the hydrogen pressure were varied between 90-140 °C and 10-80 bar, respectively. Over Ni catalysts NH3 and/or a base modifier suppressed the formation of secondary amine. High selectivity (93-98 %) to primary amine was obtained on Raney nickel, Ni/Al203 and Ru/A1203 catalysts at complete nitrile conversion. With respect to the effect of metal supported on alumina the selectivity of dodecylamine decreased in the order Co Ni Ru>Rh>Pd>Pt. The difference between Group VIII metals in selectivity can be explained by the electronic properties of d-band of metals. High selectivity to primary amine was achieved on base modified Raney Ni even in the absence of NH3. 

The selectivity of RNH2 on M/A1203 and Raney catalysts decreased in the order Co Ni Ru>Rh>Pd>Pt. This order corresponds to the opposite sequence of reducibility of metal-oxides [8] and standard reduction potentials of metalions [9], The difference between Group VIII metals in selectivity to amines can probably been explained by the difference in the electronic properties of d-bands of metals [3], It is interacting to note that the formation of secondary amine, i.e. the nucleophilic addition of primary amine on the intermediate imine can also take place on the Group VIII metal itself. Therefore, the properties of the metal d-band could affect the reactivity of the imine and its interaction with the amine. One could expect that an electron enrichment of the metal d-band will decrease the electron donation from the unsaturated -C=NH system, and the nucleophilic attack at the C atom by the amine [3], Correlation between selectivity of metals in nitrile hydrogenation and their electronic properties will be published elsewhere. 

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