Dual-oxidation-induced lattice disordering in a Prussian blue analog for ultrastable oxygen evolution reaction performance

Enriching the active sites and enhancing the intrinsic activity of a single site are two basic strategies for improving the activity toward the electrocatalytic oxygen evolution reaction (OER), and designing an advanced microstructure with a boosted pre-oxidation process can further guarantee durability toward long-term catalysis. Herein, we propose a dual oxidation strategy of a Co Prussian blue analog (Co PBA), which simultaneously achieves Co3+ active site enrichment, in situ CeO2 decoration and lattice dis-ordering with abundant undercoordinated sites, realizing highly efficient and ultrastable OER perfor-mance. The dual oxidation process can induce the enrichment of high-valence Co ions by combined chemical oxidation and d-f electron coupling compared to the singly oxidized catalysts, thereby provid-ing more active sites with enhanced intrinsic activity for the early triggered OER process. In addition, the disordered lattice can provide abundant reactive Co sites for the pre-oxidation process, thereby leading to obvious activation of the catalysts and remarkable operational stability due to the substantially accumu-lated Co3+ sites. Benefitting from the structural advantages of lattice-disordered dual-oxidized Co PBA nanocages, a low overpotential of 240 mV can be achieved for a 10 mA cm-2 current density, and the large catalytic current density and intrinsic activity are among the best compared to those of previously reported PBA-based and PBA-derived catalysts and even RuO2 and IrO2. In addition, ultrastable OER behavior with a 263 % activity enhancement in 150 h can result, making the dual-oxidized catalyst a promising candidate for water electrolysis.(c) 2022 Elsevier Inc. All rights reserved.