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Electron-Isolating Band Solidified Fe─O Bond in Ni/NiFe Layered Double Hydroxide Composite for Stable Ampere-Level
Zhangtao Guo1, Qian Zhu1, Shaohua Wang1
1State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, P. R. China.
Abstract:
The dissolution of iron ions triggers irreversible structural collapse and resultant catastrophic deactivation in NiFe-layered double hydroxides (NiFe LDHs), representing a formidable challenge to their implementation in sustainable hydrogen production. Herein, by adjusting the Ni nanoparticle content in Ni/NiFe LDH composites synthesized via reduction-coprecipitation method, Fe t2g orbital occupancy is regulated to protect the Fe─O bond from cleavage. Specifically, with considerable electron transfer from Ni to Fe t2g orbital, the low-energy antibonding of Fe t2g* band separates from the (Fe─O) bonding band, lying near and crossing the Fermi level, as evidenced by x-ray absorption spectra (XAS) and the calculated density of states. This band serves as an electron-isolating band to avoid electron removal from the (Fe─O) bonding band, which significantly solidifies the Fe─O bond confirmed by operando XAS. Additionally, the modulation lowers the adsorption energy of Cl-, suppressing the chloride-induced electrocatalyst corrosion in seawater electrolysis. Consequently, the optimal sample operates stably at 1 A cm-2 for over 10 000 h in the three-electrode system and beyond 450 h in an anion-exchange membrane water electrolyzer under simulated seawater oxidation, ranking among the state-of-the-art powder-type NiFe LDH-based catalysts. This work highlights the manipulation of antibonding orbital state for fundamentally enhancing electrocatalyst stability.
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