Abstract
The behaviors and kinetics of hydrogen evolution reaction (HER) on pure aluminum with passive film in the presence and absence of chloride ion are quantitatively investigated by using the tip generation/substrate collection mode of scanning electrochemical microscopy (SECM) with dual Al/Pt ultramicroelectrode (UME) as tip electrode and Pt UME as substrate electrode. The standard rate constants k0 and transfer coefficients αH of HER in ClO4−- and Cl−-containing solution are 6.9 × 10−7 cm/s and 0.22, 7.1 × 10−6 cm/s and 0.19, respectively. Results show that the kinetic of HER is slow and the destruction of Cl− on passive film can significantly promote the HER on Al surface. Moreover, these αH far less than commonly used 0.5 in corrosion research, can explain the great difference between theoretical Tafel slopes and experimental results. Besides, the existence of current plateau in Al electrode explains the large difference in corrosion potential during parallel testing.
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