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Mn-Induced Support Stabilization and Ir Electronic Activation Enable Acid-Stable, Low-Loading IrO2 Water Oxidation
Zhe Liu1,2,3, Guoxin Ma1, Shixiang Yu4
1State Key Laboratory of Fluorine & Nitrogen Chemicals, School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, P.R. China.
None:
The practical application of low-iridium catalysts for the acidic oxygen evolution reaction (OER) is primarily constrained by the intertwined issues of inadequate activity and stability. Incorporation of Mn into such low-iridium catalysts is effective, yet the underlying mechanism remains unclear. This study addresses the mechanistic role of Mn doping in enhancing the activity and stability of low-loading IrO2/Co3O4 catalysts. By incorporating Mn3+ into the octahedral sites of Co3O4, Mn induces strong Mn─O covalency that reinforces the spinel lattice and stabilizes ultra-low-loading IrO2 nanoparticles, delivering a 51 mV reduction in overpotential and a six-fold enhancement in operational stability compared to its undoped counterpart at a current density of 10 mA cm-2. In situ spectroscopic analyses and theoretical calculations decipher the dual role of Mn: it reinforces lattice integrity through strong covalent Mn─O bonds, suppressing ion leaching, while concurrently activating the Ir sites via interfacial Mn─O─Ir electron transfer, which optimizes intermediate adsorption and promotes the efficient oxide-path mechanism (OPM). This work demonstrates that the targeted dual-regulation of support chemistry establishes a general principle for designing high-performance, low-loading IrO2 catalysts for acidic OER.
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