Abstract
Cobalt phosphides are an emerging earth‐abundant alternative to platinum‐group‐metal‐based electrocatalysts for the hydrogen evolution reaction (HER). Yet, their stability is inferior to platinum and compromises the large‐scale applicability of CoPx in water electrolyzers. In the present study, we employed flat, thin CoPx electrodes prepared through the thermal phosphidation (PH3) of Co3O4 films made by plasma‐enhanced atomic layer deposition to evaluate their stability in acidic water electrolysis by using a multi‐technique approach. The films were found to be composed of two phases: CoP in the bulk and a P‐rich surface CoPx (P/Co>1). Their performance was evaluated in the HER and the exchange current density was determined to be j0=−8.9 ⋅ 10−5 A/cm2. The apparent activation energy of HER on CoPx (Ea=81±15 kJ/mol) was determined for the first time. Dissolution of the material in 0.5 M H2SO4 was observed, regardless of the constantly applied cathodic potential, pointing towards a chemical instead of an electrochemical origin of the observed cathodic instability. The current density and HER faradaic efficiency (FE) were found to be stable during chronoamperometric treatment, as the chemical composition of the HER‐active phase remained unchanged. On the contrary, a dynamic potential change performed in a repeated way facilitated dissolution of the film, yielding its complete degradation within 5 h. There, the FE was also found to be changing. An oxidative route of CoPx dissolution has also been proposed.
All that glitters is not gold: Despite an apparently constant current density, flat and thin CoPx model electrodes are found to be unstable in the acidic hydrogen evolution reaction (HER). Constant potential treatment did not yield an increase in dissolution rate or change in faradaic efficiency, whereas repeated potential scanning facilitated dissolution. An oxidative route of CoPx corrosion is proposed and reverse currents are claimed to accelerate dissolution. The apparent activation energy of HER on CoPx is determined to be 81±15 kJ/mol.