Tuning d-band electronic structure of Ni-Fe oxyhydroxides via doping engineering boosts seawater oxidation performance

doi:10.1016/S1872-2067(24)60255-X

Abstract

Abstract:

Seawater electrolysis holds significant importance for advancing clean energy conversion. NiFe-based catalysts exhibit outstanding performance in the oxygen evolution reaction (OER) under alkaline conditions. However, the instability of the Fe active center leads to leakage issues, hindering further development in the field of seawater electrolysis. Here, we adopt an element doping engineering strategy to enhance the OER activity of Ni-Fe oxyhydroxides and greatly stabilize the Fe sites by meticulously optimizing the d-band centers. Among the selected metals (Al, Ce, Co, Cr, Cu, Mn, Sn, Zn and Zr), Mn doping is the most effective as confirmed by both theoretical calculations and experimental verifications. The NiFeMn-OOH/NF formed in situ from the corresponding metal-organic framework requires only 217 mV to achieve a current density of 10 mA·cm^-2 in alkaline seawater, and exhibits exceptional stability. Theoretical calculations uncover that the Fe sites exhibit better balance of adsorption-desorption kinetics for OER intermediates than Ni sites and Ni-Fe dual-sites, while Mn sites with the polyvalent nature modulate the d-band center closer to Fermi level, facilitate the transfer of electrons across the catalyst surface, thus accelerating the reaction kinetics. This work is of considerable significance for achieving efficient and sustainable seawater electrolysis.

Key words: Nickel-iron oxyhydroxide, Oxygen evolution reaction, Self-reconfiguration, Seawater electrolysis, d-Band center

Liyuan Xiao, Xue Bai, Jingyi Han, Zhenlu Wang, Jingqi Guan. Tuning d-band electronic structure of Ni-Fe oxyhydroxides via doping engineering boosts seawater oxidation performance[J]. Chinese Journal of Catalysis, 2025, 71: 340-352.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60255-X

https://www.cjcatal.com/EN/Y2025/V71/I4/340

Figures/Tables 8

Fig. 1. The synthesis route of NiFeM-OOH/NF.

Fig. 2. Simulation of the basic electrochemical steps of OER at Fe site (a) and NiFe (b) sites. Volcanic curve of theoretical overpotential and OH* and O* intermediates free energy generation at Fe site (c), Ni site (d) and NiFe sites (e).

Fig. 3. (a,b) LSV curves of NiFeM-OOH/NF. Inset shows the Tafel slopes. (c) Performance comparison diagram. (d) LSV curves for NiFeMn-OOH/NF, NiFe-OOH/NF, Ni-OOH/NF, Fe-OOH/NF and Mn-OOH/NF. (e) LSV curves of NiFeMnx-OOH/NF with different Mn contents. (f) EIS spectra. (g) Arrhenius plots. (h) Chronoamperometric response of NiFeMn-OOH/NF and NiFe-OOH/NF.

Fig. 4. LSV curves (a) and Tafel slopes (b) in different electrolytes. (c) LSV curves of NiFeMn-OOH/NF and NiFe-OOH/NF in alkaline seawater. (d) Chronoamperometry of NiFeMn-OOH/NF and NiFe-OOH/NF in alkaline seawater at 200 mA·cm-2. (e) EIS spectra. (f) LSV curves of overall water splitting in alkaline seawater. Inset shows a schematic diagram of the NiFeMn-OOH/NF||Pt asymmetric electrolyzer. (g) Chronoamperometry of NiFeMn-OOH/NF||Pt electrolyzers in alkaline seawater at 10 mA·cm-2. Inset shows the LSV curves before and after the stability test.

Fig. 5. SEM images (a,b), EDS mapping (c) and HRTEM images (d,e) of NiFeMn-TPA/NF. SEM (f), EDS mapping (g) and HRTEM images (h,i) of NiFeMn-OOH/NF.

Fig. 6. (a) XRD patterns. (b) In-situ Raman spectra of NiFeMn-OOH/NF under different applied potentials. High-resolution Fe 2p (c), Ni 2p (d), Mn 2p (e) XPS spectra and O 1s XPS spectra (f).

Fig. 7. XANES spectrum (a), EXAFS spectrum (b), and WT spectrum (c) illustrating the Ni K-edge characteristics in NiFeMn-OOH. XANES spectrum (d), EXAFS spectrum (e), and WT spectrum (f) illustrating the Fe K-edge characteristics in NiFeMn-OOH. XANES spectrum (g), EXAFS spectrum (h), and WT spectrum (i) illustrating the Mn K-edge characteristics in NiFeMn-OOH.

Fig. 8. DOS diagram of NiFeOOH (a) and NiFeMnOOH (b). (c) DOS diagram of Fe-3d. (d) NiFeMn-OOH as a catalyst for cycling in OER. (e) Comparison of Fermi levels of NiFe-OOH and NiFeMn-OOH. (f) Gibbs free energy diagram for the OER on NiFeOOH and NiFeMnOOH.

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