Investigation of the interfacial properties of platinum stepped surfaces using peroxodisulfate reduction as a local probe

Peroxodisulfate (PDS) reduction has been investigated by electrochemical and FTIR techniques in a wide pH range, on platinum stepped single crystals electrodes vicinal to the (111) pole. PDS reduction is a structure-sensitive reaction and proceeds on well differentiated potential regions for terrace and step sites. This fact allows gaining local information about the individual behavior of those sites. The reaction proceeds at appreciable rate in a narrow potential range, being inhibited in the low and high potential regions of the voltammogram. The inhibition of the reaction at low potentials is most likely associated with a change in the sign of the charge on the electrode, from positive to negative. Therefore, PDS reduction gives an approximate indication of the position of the potential of zero free charge (pzfc). In this way, two local values of pzfc, associated with terrace and steps sites, can be determined. Such values of local pzfc are compared with the local values of potential of maximum entropy (pme) of double layer formation deduced from laser induced T-jump experiment. Good agreement between both magnitudes is found, especially for terraces. The local pzfc on terraces shifts to more positive potentials as the terrace length diminishes, while the local pzfc for steps remains constant. The inhibition of PDS reduction at high potentials can also be related with a second inversion in the sign of the electrode charge. Therefore, PDS reduction can be used to determine a second pzfc on the (111) terraces at high potentials, revealing a non-monotonic charge – potential relationship. Spectroscopic experiments allow the identification of the species involved in PDS reduction. •Peroxodisulfate reduction is investigated on platinum stepped single crystal surfaces.•This reaction is sensitive to the crystallographic structure of the surface.•The rate of the reaction is sensitive to the local nature of the charge on the surface.•This allows detection of local values of the potential of zero free charge.•The dependence of local values of potential of zero charge on terrace length is investigated.