Mesoscopic mass transport effects in electrocatalytic processes.

The role of mesoscopic mass transport and re-adsorption effects in electrocatalytic reactions was investigated using the oxygen reduction reaction (ORR) as an example. The electrochemical measurements were performed on structurally well-defined nanostructured model electrodes under controlled transport conditions in a thin-layer flow cell. The electrodes consist of arrays of Pt ultra-microelectrodes (nanodisks) of defined size (diameter approximately 100 nm) separated on a planar glassy carbon (GC) substrate, which were fabricated employing hole-mask colloidal lithography (HCL). The measurements reveal a distinct variation in the ORR selectivity with Pt nanodisk density and with increasing electrolyte flow, showing a pronounced increase of the H2O2 yield, by up to 65%, when increasing the flow rate from 1 to 30 microL s(-1). These results are compared with previous findings and discussed in terms of a reaction model proposed recently (A. Schneider et al., Phys. Chem. Chem. Phys., 2008, 10, 1931), which includes (i) direct reduction to H2O on the Pt surface and (ii) additional H2O2 formation and desorption on both Pt and carbon surfaces and subsequent partial re-adsorption and further reduction of the H2O2 molecules on the Pt surface. The potential of model studies on structurally defined catalyst surfaces and under well-defined mass transport conditions in combination with simulations for the description of electrocatalytic reactions is discussed.