Probing the hydrogen adsorption affinity of Pt and Ir by surface interrogation scanning electrochemical microscopy (SI-SECM)

Scanning electrochemical microscopy in the surface interrogation mode (SI-SECM) has been used to probe the strength of metal-adsorbed H bonds at Pt and Ir. The generally accepted view is that this technique can only give meaningful results for similar probe and substrate electrode dimensions. However, it is shown that SI-SECM can also provide valuable information for H adsorption even when the substrate is much larger than the microelectrode probe (of 500 and 25 μm diameter respectively), for properly chosen substrate and mediator combinations that minimize the tip currents under substrate open circuit potential conditions. Linear sweep voltammetry at a microelectrode positioned at a very small probe–substrate distance (2.5 μm) showed remarkable positive feedback in the presence of an oxidizable mediator (TMPD) when a full or partial H monolayer was electrochemically pre-formed on the Pt or Ir substrate. The magnitude and shapes of chronoamperometric responses at the tip were interpreted in terms of variation of H coverage with time and changes in the open circuit potential of the substrate. The higher affinity of Ir than Pt for adsorbed H has been used to validate the approach.