Electrocatalytic Oxidation of Ethanol and Formic Acid on Bimetallic Nanoalloys and Core-Shell Nanoparticles

Mechanism of ethanol electrooxidation on numerous materials has been widely investigated in the past. It is well known that in acidic conditions the electrooxidation of ethanol on platinum surface leads to strongly adsorbed surface groups (i.e. CO), poisoning the surface of catalyst and inhibiting further reactions. Presence of metals other than platinum will make it possible to oxidize adsorbed CO by surface OH groups, present on the other metal (so called “bi-functional mechanism”). Such bi-metallic surface is more resistant to poisoning and as a result more catalytically active. Hovewer it is still not well understood, how the presence of the other metal influences the surface’s electronic properties, which in turn alter adsorption properties, and reaction mechanism.

Electronic properties of the catalyst can be modified by the following methods: they can be related directly to charge transfer from other component of the system, such as another component of the alloy, from substrate, or they can be induced by geometric factors, such as change in lattice parameter. Change in lattice parameter influences the degree of overlapping of valence orbitals forming the conduction band. When lattice is contracted, the conduction band becomes broader. When the conduction band is filled in more than half the broadening of the conduction band leads to shift of the d-band center towards Fermi edge. The lattice parameter can be (to some degree) modified, and as a result, the degree of orbital overlapping can be changed, for instance by alloying.  It is known that in alloys the atom-atom distance changes linearly as a function of composition, in the range determined by inter-atomic distances of the pure elements (Vegard’s law). Similarly, when thin layers are formed, the layer forming metal will exhibit the lattice parameter of the substrate (so called “pseudomorphic monolayer”). Consequently experimental investigation of materials, where lattice parameter has been intentionally modified, allows for experimental determination of the relation between reaction mechanism and electronic properties of the material used.