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

Abstract

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 disordering with abundant undercoordinated sites, realizing highly efficient and ultrastable OER performance. 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 providing 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 accumulated Co3+ sites. Benefitting from the structural advantages of lattice-disordered dual-oxidized Co PBA nanocages, a low overpotential of 240mV can be achieved for a 10mAcm-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 150h can result, making the dual-oxidized catalyst a promising candidate for water electrolysis.