Electrocatalytic Properties of Ni-Based Alloys Toward Hydrogen Evolution Reaction in Acid Media

The electrocatalytic performance toward the hydrogen evolution reaction (HER) of a series of Ni-based alloys prepared by electroless deposition was studied by means of linear polarization, cyclic voltammetry, and potential step techniques. Ni-W-P and Ni-Mo-P alloy electrodes exhibit good electrocatalytic activity toward HERs, with some Ni-Mo-P alloys approaching the performance of Pt foils. The electrocatalytic activity of Ni-based alloys decreases with increasing P content but increases with increasing content of W or Mo. The experimental results can be interpreted in terms of a pronounced synergy between Ni, which has internally paired d electrons, and W or Mo, which have empty or half-filled d orbitals and therefore, bind hydrogen atoms strongly. The absorption of hydrogen in these alloys is also found to have an important effect on their activity. Electrodes with higher activity are capable to incorporate larger amounts of hydrogen during cathodic charging. © 2003 The Electrochemical Society. All rights reserved.