In Situ Regulating Cobalt/Iron Oxide‐Oxyhydroxide Exchange by Dynamic Iron Incorporation for Robust Oxygen Evolution at Large Current Density

• Published in: Advanced materials (Weinheim) 2024-02, Vol.36 (5), p.e2305685-n/a
• Main Authors: Li, Dongyang, Xiang, Rong, Yu, Fang, Zeng, Jinsong, Zhang, Yong, Zhou, Weichang, Liao, Liling, Zhang, Yan, Tang, Dongsheng, Zhou, Haiqing
• Format: Article
• Language: English
• Subjects: Bimetals; Catalysts; Current density; Density functional theory; Durability; electrocatalyst; Ferric hydroxide; Green hydrogen; Heterostructures; Hydrogen production; in situ characterization; Industrial water; Iron oxides; Noble metals; non‐noble; oxygen evolution reaction; Oxygen evolution reactions; Photoelectrons; Raman spectroscopy; Robustness; Self-assembly; Transition metals; water electrolysis; Water splitting; X ray photoelectron spectroscopy
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202305685

The key dilemma for green hydrogen production via electrocatalytic water splitting is the high overpotential required for anodic oxygen evolution reaction (OER). Co/Fe‐based materials show superior catalytic OER activity to noble metal‐based catalysts, but still lag far behind the state‐of‐the‐art Ni/Fe‐based catalysts probably due to undesirable side segregation of FeOOH with poor conductivity and unsatisfied structural durability under large current density. Here, a robust and durable OER catalyst affording current densities of 500 and 1000 mA cm−2 at extremely low overpotentials of 290 and 304 mV in base is reported. This catalyst evolves from amorphous bimetallic FeOOH/Co(OH)2 heterostructure microsheet arrays fabricated by a facile mechanical stirring strategy. Especially, in situ X‐ray photoelectron spectroscopy (XPS) and Raman analysis decipher the rapid reconstruction of FeOOH/Co(OH)2 into dynamically stable Co1‐xFexOOH active phase through in situ iron incorporation into CoOOH, which perform as the real active sites accelerating the rate‐determining step supported by density functional theory calculations. By coupling with MoNi4/MoO2 cathode, the self‐assembled alkaline electrolyzer can deliver 500 mA cm−2 at a low cell voltage of 1.613 V, better than commercial IrO2(+)||Pt/C(‐) and most of reported transition metal‐based electrolyzers. This work provides a feasible strategy for the exploration and design of industrial water‐splitting catalysts for large‐scale green hydrogen production. An exceptional and stable oxygen‐evolving electrocatalyst is developed from self‐reconstruction of amorphous bimetallic FeOOH/Co(OH)2 microsheet arrays through a mechanical stirring strategy, yielding a current densities of 500 and 1000 mA cm−2 at low overpotentials of 290 and 304 mV. This catalyst rapidly reconstructs into Co1‐xFexOOH species through in situ iron incorporation into CoOOH as confirmed by in situ X‐ray photoelectron, Raman spectroscopic studies, and theoretical calculations.