Constructing highly active Co sites in Prussian blue analogues for boosting electrocatalytic water oxidation

High-valence cobalt sites are considered as highly active centers for the oxygen evolution reaction (OER) and their corresponding construction is thus of primary importance in the pursuit of outstanding performance. Herein, we report the design and facile synthesis of abundant high-valence cobalt sites by introducing Zn²⁺ into CoFe Prussian blue analogues (PBAs). The modification results in the drastic morphological transformation from a pure phase (CoFe-PBA) to a three-phase composite (CoFeZn-PBA), with a significant increase not only the amount of highly oxidized Co sites but the specific surface area (by up to 4 times). Moreover, the obtained sample also exhibits outstanding electric conductivity. Consequently, an excellent OER performance with an overpotential of 343 mV@10 mA cm^-2 and a Tafel slope of 75 mV dec^-1 was achieved in CoFeZn-PBA, which outperforms the commercial IrO₂ catalyst. Further analysis reveals that CoFeZn-PBA becomes (oxyhydr)oxides after the OER.