ABSTRACT
Prussian blue analogs (PBAs) are promising catalysts for green hydrogen production. However, the rational design of high-performing PBAs is challenging, which requires an in-depth understanding of the catalytic mechanism. Here FeMn@CoNi core-shell PBAs are employed as precursors, together with Se powders, in low-temperature pyrolysis in an argon atmosphere. This synthesis method enables the partial dissociation of inner FeMn PBAs that results in hollow interiors, Ni nanoparticles (NPs) exsolution to the surface, and Se incorporation onto the PBA shell. The resulting material presents ultralow oxygen evolution reaction (OER) overpotential (184 mV at 10 mA cm-2 ) and low Tafel slope (43.4 mV dec-1 ), outperforming leading-edge PBA-based electrocatalysts. The mechanism responsible for such a high OER activity is revealed, assisted by density functional theory (DFT) calculations and the surface examination before and after the OER process. The exsolved Ni NPs are found to help turn the PBAs into Se-doped core-shell metal oxyhydroxides during the OER, in which the heterojunction with Ni and the Se incorporation are combined to improve the OER kinetics. This work shows that efficient OER catalysts could be developed by using a novel synthesis method backed up by a sound understanding and control of the catalytic pathway.
ABSTRACT
Prussian blue analogs (PBAs) are considered as efficient catalysts for energy-related applications due to their porous nanoscale architectures containing finely disseminated active sites. Their catalytic capability can be greatly boosted by the rational design and construction of complex PBA hybrid nanostructures. However, present-day structure engineering inevitably involves additional etchant or procedure. Herein, a facile, yet controllable one-pot self-assembly strategy is introduced to prepare hierarchical core-shell polymetallic PBAs (featuring bimetallic FeMn PBAs cores and CoNi PBAs shells) with hollow nano-cages/solid nano-cube architectures. The detailed characterization of material morphology/composition, assisted with theoretical simulations, reveals the underlying formation mechanism where the key factor is the control of the nucleation rate via the use of chelating agent (citrates) and reaction kinetics. The resulting FeMn@CoNi-H compound is found to accelerate the oxygen evolution reaction activity with a low overpotential (236 mV at a current density 10 mA cm-2 ) as well as a low Tafel slope (58.4 mV dec-1 ). Such an impressive performance is endowed by the rational compositional and structural design with optimized electronic structures as well as an increase in exposed active sites. This work provides a robust, cost-effective pathway that enables chemical and morphological control in creating high-performance catalysts for water electrolysis.
