In
transition metal-based alloys, the nonlinearity of the current
at large cathodic potentials reduces the credibility of the linear
Tafel slopes for the evaluation of electrocatalytic hydrogen activity.
High-precision nonlinear fitting at low current densities describing
the kinetics of electrochemical reactions due to charge transfer can
overcome this challenge. To show its effectiveness, we introduce a
glassy alloy with a highly asymmetric energy barrier: amorphous NiP
electrocoatings (with different C and O inclusions) via changing the
applied DC and pulsed current and NaH2PO2 content.
The highest hydrogen evolution reaction (HER) activity with the lowest
cathodic transfer coefficient α = 0.130 with high J
0 = −1.07 mA cm–2 and the largest
surface areas without any porosity are observed for the pulsed current
deposition. The calculated α has a direct relation with morphology,
composition, chemical state and coating thickness defined by the electrodeposition
conditions. Here, a general evaluation criterion with practicality
in assessment and high accuracy for electrocatalytic reactions applicable
to different metallic alloy systems is presented.