Pt electrode corrosion in concentrated sulfuric acid has been studied by a series of electrochemical measurements in combination with instrumental analyses. It has been found that the cathodic polarization of Pt in 16∼18 mol dm
−3 H
2SO
4 generates sulfur deposition on the Pt electrode. The following anodic polarization induces sulfur dissolution and Pt corrosion. SEM-EDS, XPS and EQCM results well-supported that the electrochemical behaviors occurred at the Pt electrode. The sulfur deposition was proven to take place by H
2SO
4 reduction at −0.08∼+0.02 V
vs. SHE and sulfur dissolution at +1.32∼+1.52 V
vs. SHE, which indirectly causes Pt corrosion. The RRDE result confirmed that Pt corrosion takes place via a two-step electrode reaction at +1.62∼+1.92 V
vs. SHE and +1.12∼+1.32 V
vs. SHE. As a result of Pt corrosion, no Pt was detected in the electrolytic solution, but was found to yield a Pt-S composite accumulated on the electrode. The Pt corrosion mechanism in the concentrated sulfuric acid was thus found to be complicated, which is far from the simple Pt ionization predicted in the Pourbaix's diagram.
View full abstract