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Previous work on the electrochemistry of palladium in aqueous acid solution demonstrated the existence of two multilayer hydrous oxide reduction peaks, one at ca. 0.24 V and another at ca. 0.55 V vs. RHE, plus the presence of a reversible active surface state transition at ca. 0.24 V. In the present work with thermally activated palladium it was observed that, in agreement with the hydrous oxide reduction behaviour of the system, there is a second active state transition at E≥ca. 0.45 V. In most of its reactions in aqueous acid solution, apart from its unusual capacity to absorb hydrogen, palladium exhibits properties very similar to those of platinum; however, palladium seems to be more prone to dissolution and subsurface oxygen formation. Also the premonolayer oxidation responses of these two metals are often different as the more active state of the palladium surface is not as readily generated as that of platinum. The electrocatalytic properties of palladium, as reported earlier, correlate quite well with the hydrous oxide and premonolayer oxidation behaviour of this electrode system.

It is now well established that gold, in the form of oxide-supported microparticles or even as conventional macroelectrodes, displays inexplicably high catalytic activity for some reactions. In the present work, gold surfaces were superactivated by a combination of thermal and cathodic pretreatment and such electrodes in base yielded up to five distinct, and quite marked, premonolayer oxidation responses within the double layer region, over the range 0.0–1.0 V (RHE). As outlined in earlier publications, such unusual behaviour is important from an electrocatalytic (and heterogeneous catalysis) viewpoint. A new mode of active site adsorption, involving highly localized electron transfer from active surface atoms to either the external circuit (in electrocatalysis) or an adsorbing reactant (in heterogeneous catalysis), is proposed. Such localized (active site) adsorption, which is based on surface quantum confinement effects, is virtually independent of (or only indirectly related to) the electronic properties of the bulk metal.

Severe thermal pretreatment of gold wire electrodes in an inert gas atmosphere resulted in the appearance of dramatic premonolayer oxidation responses, which in some instances commenced at 0.25 V (RHE), for the resulting active gold electrodes in aqueous acid media. Similar behaviour was reported earlier for platinum and gold activated by cathodic pretreatment in acid solution; these active noble metal surfaces are evidently more susceptible to oxidation than bulk copper. Such behaviour was attributed to the effect of surface disorder; many of the metal atoms at the interface are assumed to be in a very active, metastable state possessing quite low lattice stabilization energy. Premonolayer oxidation responses are again correlated with electrocatalytic behaviour and the existence of unusual chemisorption behaviour for molecules reacting at highly active states of metals is outlined.

The present work is a continuation of an earlier investigation of the effect of severe thermal pretreatment on the redox properties of platinum electrodes in aqueous media. The most interesting observation was that raising the solution temperature to ca. 75 °C resulted in a dramatic anodic response in the positive sweep at ca. 0.25 V (RHE). Such behaviour was noted earlier at room temperature but only when the thermally pretreated sample was further activated by cathodic polarization. This transition at 0.25 V was partially reversed on the negative sweep, but the cathodic process involved was subject to severe inhibition. There is independent evidence for similar behaviour for gold in aqueous acid solution. The relevance of the present results to the operation of fuel cell anodes is outlined.