The effect of Pt surface orientation on the oscillatory electro-oxidation of glycerol

In the present paper, we have studied the influence of (bi)sulfate anion (0.1 and 0.5 M) on the electro-oxidation of glycerol on basal Pt(hkl) and stepped surfaces belonging to the series of Pt(S)[n(1 1 1) x (11 1)]. Cyclic voltammograms and derivative voltammetry pointed out that the catalytic activity decreases for Pt(1 1 1) and Pt(1 1 0) and, to a minor extent, for stepped surfaces in 0.5 mol/L H2SO4. Chronoamperometric curves demonstrated that above 0.60 V (vs RHE), for both concentrations (0.1 and 0.5 mol/L H2SO4), stepped surfaces and Pt(1 1 0) showed greater ability to catalyze the glycerol electro-oxidation in comparison with Pt(1 1 1). Potential oscillations were mapped along with slow galvanodynamic sweeps and studied at constant current. For Pt(1 1 1), no oscillations were found in the galvanodynamic regime, however, under the galvanostatic regime, period 1 oscillations were observed after a long induction period. The oscillations showed a very sim-ilar profile for stepped surfaces, even for the Pt(3 3 2) surface, which has a high density of (1 1 0) steps. Pattern changes were observed only for Pt(1 1 0) compared to other surfaces. Therefore, we conclude that (1 1 0) step sites influence the oscillatory behavior, thus the insertion of the steps favors the path of formation of inactive species, which compete for the same catalytic sites in a given potential region. The extinction of the mechanism oscillatory occurs differently due to the intrinsic characteristics of each surface electrode for the formation of (hydro)oxides.

Automated summary

The influence of (bi)sulfate anion on the electro-oxidation of glycerol on Pt(hkl) surfaces was studied. The results showed that stepped surfaces and Pt(1 1 0) exhibited higher catalytic activity in high concentration sulfuric acid solution, and the presence of (1 1 0) step sites influenced the oscillatory behavior.