LAUSR

Abstract Here, a reduction‐cation exchange (RCE) strategy is proposed for synthesizing Fe–Co based bimetallic Prussian blue analogs (PBAs) with heterogeneous composition distribution and open cage nanocage architecture. Specially, bivalent cobalt is introduced into a potassium ferricyanide solution containing hydrochloric acid and polyvinyl pyrrolidone. The uniform PBAs with opened cages are formed tardily after hydrothermal reaction. Time‐dependent evolution characterization on composition elucidating the RCE mechanism is based on the sequential reduction of ferric iron and cation exchange reaction between divalent iron and cobalt. The PBA structures are confirmed by electron tomography technology, and the heterogeneous element distribution is verified by energy‐dispersive X‐ray spectroscopy elemental analysis, leading to the formation of core–shell PBAs with compositional heterogeneity (Fe rich shell and Co rich core) and open cage architecture. When the PBA catalysts are used to boost the oxygen evolution reaction (OER), superior OER activity and long‐term stability (low overpotential of 271 mV at 10 mA cm−2 and ≈5.3% potential increase for 24 h) are achieved, which is attributed to the unique compositional and structural properties as well as high special surface areas (576.2 m2 g−1). The strategies offer insights for developing PBAs with compositional and structural multiplicity, which encourages more practical catalytic applications.