Supported metals alloying effects

We have overviewed some strategies for the surface-mediated fabrication of metal and alloy nanoscale wires and particles in mesoporous space, and their structural characterization and catalytic performances. Extension of the present approaches for metal/alloy nanowires may lead to the realization of the prospechve tailored design of super active, selective and stable catalysts applicable in industrial processes. The organometallic clusters and nanowires offer exciting and prospechve opportunities for the creahon of new catalysts for industry. Various metal/ alloy nanowires and nanoparhcles in the anisotropic arrangement in porous supports would help in understanding the unexpected electronic and optic properties due to the quantum effect, which are relevant to the rational design of advanced electronic and optic devices. 

Copper-catalysts promoted with i) other group VIA or VIIIA metals and ii) alcaline or alcaline earth elements (IA or IIA) are used for selective hydrogenation of various organic compounds (1). Moreover Cu(Co) Zn-Al catalysts were extensively studied for the synthesis of methanol and of light alcohols (2,3). More recently, due to the development of fine chemical processes, detailed studies of copper catalysts were carried out in order to show, like for noble metals, the effect of supports (SMSI), of promoters and of activation-on metal dispersion or reduction, on alloy formation... For example modified copper catalysts are known for their utilization in the dehydrogenation of esters (4-6), in the hydrolysis of nitriles (7), in the selective hydrogenation of nitriles (8), in the amination of alcohols (9)... 

Is it known that the rate of hydrogenolysis reactions are extremely sensitive to effects of alloying, surface contamination, poisoning, etc. Consequently, in all cases where supported metals are used there must be concern as to whether apparent particle size effects are due to structure sensitivity or to some minor contamination effect. In the few cases where clean single crystal surfaces have been used there is evidence of a structure effect.338 However, the maximum change in activity between different crystal faces seems to be about a factor of 10. For Ni single crystals the (100) surface is more active than the (111) surface. A similar conclusion has been reached for oriented Ni powder samples.339... 

Cementation consists in the formation of a surface alloy with a less reactive metal. For zinc, alloying can be effected with mercury (amalgamation), copper, silver, nickel.12 The reactivity of a cemented metal can be explained considering that the supporting metal plays only the role of an electron reservoir, the true chemistry is effected by the superficial additional metal. Zinc can also be activated by washing with aqueous ammonium chloride,13 or by reacting the powder with trimethyl-chlorosilane.14 In this latter case, Barbier reactions were effected even at 0°C in short times. The activation mechanism was not determined. 

Bezerra et al extensively reviewed heat treatment and stability effects of various Pt/C, Pt-M/C, and C-supported Pt-free alloy catalysts, taking into account particle sizes and stiuctural parameters. Appropriate heat treatment of Pt/C catalysts improves ORR activity by stabilizing the carbon support against corrosion, which in turn increases the cathode life time. Depositing mixed-metal Pt monolayers on carbon-supported metal nanoparticles or Pt monolayers on noble/non-noble core-shell nanoparticles leads to enhanced electrode performance. RRDE experiments on the catalytic activity of Pt-M (M = Au, Pd, Rh, Ir, Re or Os) monolayers on carbon-supported Pd nanoparticles showed that an 80 20 PtiM ratio for the nuxed monolayers performs better than commonly nsed Pt/C catalysts. ... 

By using metal as the capping layer, SPPs have been demonstrated as an effective means for increasing the external quantum efficiency of ZnO. The use of thin spacer and metal alloy can eliminate the unwanted Forster energy transfer and support on-resonance SPP coupling. In addition, nanocrystalline Au can on one hand suppress the deep-level emission while on the other hand increase the band-edge emission of ZnO. Finally, the radiative SPP arising from MIM can be used to increase the forward emission of ZnO. 

Some aspects of the particle size, alloying effect, and metal-support interaction in nano-sized supported metal particles are presented for the oxidation of ethylene, the hydrogenolysis of alkanes, and the hydrogenations of unsaturated hydrocarbons and a,j8-unsaturated aldehydes. The influence of these phenomena is highlighted on the... 

There is no single interpretation to explain the effects of particle size, alloying, and metal-support interaction on the chemisorption and catalytic properties of supported metal particles. Depending on the particle size, the nature of co-metal and support, and the nature of the reaction, the change of chemisorption and catalytic properties can be interpreted in terms of geometric features, electronic modifications, and/or mixed sites. This is due to the formation of various adsorbed species and intermediates. Moreover, in many cases, the promotion of catalytic properties will be directly related to the method of catalyst preparation, which affects the architecture of the active site, with respect to chemical and electronic states of components and topology. 

Three aspects of the performance of supported catalysts are also discussed in this Chapter. With the development of techniques, as outlined above, for the characterization of supported metal catalysts, it seems timely to survey studies of crystallite size effect/structure sensitivity with special reference to the possible intrusion of adventitious factors (Section 5). Recently there has been considerable interest in the existence of (chemical) metal-support interactions and their significance for chemisorption and catalytic activity/ selectivity (Section 6). Finally, supported bimetallic catalysts are discussed for various reactions not involving hydrocarbons (hydrocarbon reactions over alloys and bimetallic catalysts have already been reviewed in this Series with respect to both basic research and technical applications ). References to earlier reviews (including some on techniques) that complement material in this Chapter are given in the appropriate sections. It might be useful, however, to note here some topics not discussed that also form part of the vast subject of supported metal and bimetallic catalysts and for which recent reviews are available, viz, spillover, catalyst deactivation, the growth and... 

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