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Understanding the Hydrogen Evolution Reaction Kinetics of Electrodeposited Nickel‐Molybdenum in Acidic, Near‐Neutral, and Alkaline Conditions
Author(s) -
Bao Fuxi,
Kemppainen Erno,
Dorbandt Iris,
Bors Radu,
Xi Fanxing,
Schlatmann Rutger,
Krol Roel,
Calnan Sonya
Publication year - 2021
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.202001436
Subject(s) - tafel equation , exchange current density , chemistry , cyclic voltammetry , kinetics , electrolyte , inorganic chemistry , nickel , molybdenum , dielectric spectroscopy , catalysis , electrochemical kinetics , electrochemistry , double layer capacitance , platinum , linear sweep voltammetry , hydrogen , electrode , organic chemistry , physics , quantum mechanics
Nickel‐molybdenum (NiMo) alloys can be a possible alternative to platinum as hydrogen evolution reaction (HER) catalysts because of the superior HER activity. However, the superior HER activity and the pH‐dependent kinetics are not currently fully understood. Herein, we present a study of HER kinetics and mechanisms of NiMo in alkaline, near‐neutral and acidic media by combining voltammetry measurements with electrochemical impedance spectroscopy and a microkinetic model. The results indicate that, compared to Ni, NiMo has significantly higher active surface area and intrinsic HER activity. In the subsequent measurements, we demonstrated that different from the existing explanations to the HER mechanisms for NiMo, the HER process in acidic, near‐neutral, and alkaline media is controlled by the Heyrovsky step. Our results show that increasing pH increases the hydrogen coverage, which increases the Tafel‐slope at low overpotentials, eventually resulting in only a single Tafel slope, which would commonly be interpreted as a Volmer‐limited reaction. Furthermore, the studies of thickness effect on HER kinetics show that the HER kinetics of NiMo are thickness‐dependent. In phosphate buffer, the increase in thickness did not significantly increase the double‐layer capacitance, but simulations with the microkinetic model indicate that the active surface area still increased similarly to other electrolytes, which is likely related to the type of electrolyte used.