Requirements for beneficial electrochemical restructuring: A model study on a cobalt oxide in selected electrolytes

TL;DR

This study investigates how electrolyte composition influences the electrochemical restructuring of a cobalt-based catalyst into an active OER catalyst, revealing key factors for designing high-performance electrocatalysts.

Contribution

It demonstrates the electrolyte-dependent restructuring kinetics and identifies the local order, oxidation state, and active sites as crucial for catalyst performance.

Findings

Only carbonate electrolyte activated the catalyst effectively.

Restructuring kinetics vary significantly with electrolyte anions.

Final catalyst shows high Co oxidation state and many redox-active sites.

Abstract

The requirements for beneficial materials restructuring into a higher performance OER electrocatalyst are still a largely open question. Here we use Erythrite (Co$_3$(AsO$_4$)$_2\cdot$8H$_2$O) as a Co-based OER electrocatalyst to evaluate its catalytic properties during in-situ restructuring into an amorphous Co-based catalyst in four different electrolytes at pH 7. Using diffraction, microscopy and spectroscopy, we observed a strong effect in the restructuring kinetics depending of the anions in the electrolyte. Only carbonate electrolyte could activate the catalyst electrode, which we relate to its slow restructuring kinetics. While its turnover frequency (TOF) reduced from 2.84 O$_2$ Co$^{-1}$ s$^{-1}$ to a constant value of 0.10 O$_2$ Co$^{-1}$ s$^{-1}$ after 300 cycles, the number of redox active sites continuously increased, which explained the current increase of around 100%. The final activated material owns an adequate local order, a high Co oxidation state and a high number of redox-active Co ions, which we identify as the trinity for enhancing the OER activity. Thus, this work provides new insights into for the rational design of high-performance OER catalysts by electrochemical restructuring.