Abstract
The electrocatalysis of alloys between Pd and Group IB metals (Pd + IB alloys) towards the oxidation of formate and formaldehyde in 1.0 M NaOH has been investigated. Pd + IB alloy electrodes exhibit roughly an additivity character with respect to the component metals in their electrocatalytic activity. Pd-rich alloy electrodes are highly active towards oxidation of formate, while those rich in Group IB metals, especially Au and Cu, are active towards formaldehyde. Hydrogen gas is liberated from Group IB metals during the oxidation of formaldehyde even at potentials positive to the RHE, but it is oxidized simultaneously on the Pd+IB alloy electrodes with a bulk Pd content of more than 70 at.% for Pd + Cu or 50 for both Pd + Ag and Pd + Au. A moderate synergistic effect is seen with a maximum activity at 50 to 70 and 20 at.% Pd in the oxidation of formate on Pd+Au alloys and in the oxidation of formaldehyde on Pd + Cu alloys, respectively. The higher the electrocatalytic activity, the lower is the activation energy, but the effect is compensated partly by an accompanying decrease of the pre-exponential factor. The compensation is more extensive in the oxidation of HCHO.
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