Assembly of a Highly Active Iridium-Based Oxide Oxygen Evolution Reaction Catalyst by Using Metal–Organic Framework Self-Dissolution

The proton exchange membrane (PEM) electrolyzer for hydrogen production has multiple advantages but is greatly restricted by expensive iridium and sluggish oxygen evolution reaction (OER) kinetics. The most promising way to reduce the precious metal loading is to design and develop highly active Ir-based catalysts. In this study, a versatile approach is reported to prepare a hybrid in the form of a catalyst-support structure (Fe-IrO_x@α-Fe₂O₃, abbreviated Ir@Fe-MF) by utilizing the self-dissolving properties of Fe-MIL-101 under aqueous conditions. The formation of this hybrid is mainly due to the Ir⁴⁺ and released Fe³⁺ ions coprecipitated to assemble into Fe-IrO_x nanoparticles, and the Fe³⁺ released from the inward collapse of the metal-organic framework (MOF) spontaneously forms α-Fe₂O₃. The prepared Ir@Fe-MF-2 hybrid exhibits enhanced catalytic activity toward OER with a lower onset potential and Tafel slop, and only 260 mV overpotential is required to drive the current density to reach 10 mA cm^-2. The performed characterizations clearly indicate that the IrO₆ coordination structure is changed significantly by Fe incorporated into the IrO₂ lattice. The performed X-ray adsorption spectra (XAS) provides evidence that Ir 5d orbital degeneracy is eliminated because of multiple orbitals being semi-occupied in the presence of Fe, which is mainly responsible for the enhancement of OER activity. These findings open an opportunity for the design and preparation of more efficient OER catalysts of transition metal oxides by utilization of the MOF materials. It should be highlighted that a long-term stability of this catalyst run at a high current density in acidic conditions still faces great challenges.