Mixed platinum–gold electrocatalysts for borohydride oxidation prepared by the galvanic replacement of nickel deposits

Mixed platinum/gold coatings were prepared by partial galvanic replacement of nickel layers that had been electrodeposited onto glassy carbon electrode substrates. The process (termed “transmetalation”) involves the spontaneous replacement of surface Ni atoms by Pt and Au upon immersion of the former metal into equimolar mixed chloroplatinic and chlorolaurate acid solutions. The multimetallic deposits on glassy carbon substrates, PtAu(Ni)/GC, were characterised by SEM/EDS, XRD, AES and electrochemical techniques. Smooth films with a bulk composition enriched in Au and minimum quantities of Ni left were obtained. Pt and Au were found to be alloyed and both Pt and Au to co-exist with Ni down to the core of the layers. The PtAu(Ni) deposits displayed typical Pt and Au surface electrochemistry indicating the formation of a continuous noble metal shell; the estimated electroactive surface areas point again to an excess of Au on the surface. The activity of the PtAu(Ni)/GC electrodes towards the oxidation of borohydride was studied by voltammetry at a rotating disc electrode, RDE, and compared to that of bulk Pt and Au. As expected, the Pt–Au alloy catalyst showed behaviour intermediate to that of its pure components. However, in the limiting current potential range the alloy tended more to bulk Au behaviour (number of electrons was closer to eight) while at low overpotentials it resembled the catalytic activity of pure Pt.