Mixed metals electronic effect

The electrochemical behavior of heterometallic clusters has been reviewed clsewbcre."" The interest in examining clusters stems from their potential to act as "electron sinks " in principle, an aggregate of several metal atoms may be capable of multiple redox state changes. The incorporation of heterometals provides the opportunity to tune the electrochemical response, effects which should be maximized in very mixed"-metal clusters. Few very mixed -metal clusters have been subjected to detailed electrochemical studies the majority of reports deal with cyclic voltammetry only. Table XII contains a summary of electrochemical investigations of "very mixed"-metal clusters. 

The experimental results described in this review support the concept that, in certain reactions of the redox type, the interaction between catalysts and supports and its effect on catalytic activity are determined by the electronic properties of metals and semiconductors, taking into account the electronic effects in the boundary layer. In particular, it has been shown that electronic effects on the activity of the catalysts, as expressed by changes of activation energies, are much larger for inverse mixed catalysts (semiconductors supported and/or promoted by metals) than for the more conventional and widely used normal mixed catalysts (metals promoted by semiconductors). The effects are in the order of a few electron volts with inverse systems as opposed to a few tenths of an electron volt with normal systems. This difference is readily understandable in terms of the different magnitude of, and impacts on electron concentrations in metals versus semiconductors. 

The criterium that the mean free path should be larger than the superconducting coherence length must be met. This is a very strict condition that implies also that the impurity interband scattering rate yab should be very small yah (1/2 )(KB/ft)Tc. Therefore most of the metals are in the dirty limit where the interband impurity scattering mixes the electron wave functions of electrons on different spots on bare Fermi surfaces and it reduces the system to an effective single Fermi surface. 

Temperature independent electron tunneling was observed also in Ref. [319], where the rate of electron transfer over large distance in mixed-metal hemoglobin hybrids [MP, FeIU(CN )P], where M = Zn or Mg, was measured in the temperature range from ambient to 100 K. The electron transfer from the triplet state of MP to Fera was not effected by the freezing of the cryosolvent, which may indicate that coupling of electron transfer to low-frequency solvent modes may be minimal. For both M, but especially for M = Mg, the rate constant of the back reaction is nearly temperature independent. 

Cathodes are usually made of copper, nickel, Monel metall, electron, graphite, steel or silver. They are either perforated or made of gauze to permit an effective circulation of the electrolyte. Diaphragms, too, are made of copper, iron, electron or Monel metal. They are necessary to prevent the gases from mixing and... 

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