Sarac, BaranKarazehir, TolgaMicusik, MatejHalkali, CelineGutnik, DominikOmastova, MariaSarac, A. Sezai2025-01-062025-01-0620211944-824410.1021/acsami.1c030072-s2.0-85106365122https://doi.org/10.1021/acsami.1c03007https://hdl.handle.net/20.500.14669/1502In 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 ? = 0.130 with high J0 = -1.07 mA cm-2 and the largest surface areas without any porosity are observed for the pulsed current deposition. The calculated ? 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. © 2021 American Chemical Society.eninfo:eu-repo/semantics/closedAccessamorphous alloysButler-Volmer equationelectrodepositionenergy-dispersive X-ray analysislinear sweep voltammetrymorphologynickel phosphideRaman spectroscopyArticle237012033982559Q12368913