Activating synergetic adsorbate evolution and lattice oxygen mechanisms in NiFe-LDH via M-O-Si bonding for improved oxygen evolution reaction

doi:10.1016/S1872-2067(26)65225-4

Abstract

Abstract:

High overpotential oxygen evolution reactions (OER) remain a strongly challenging factor for efficient hydrogen production via water electrolysis in energy harvesting devices. Here, we propose a new strategy for lowering overpotentials based on M-O-Si (M=Ni, Fe) covalent bond formation through a rapid 30-s chemical etching process to create a silicon-doped anemone-like NiFe layered double hydroxide (Si-NiFe-LDH/NF). Our strategy decreases the catalytic phase-transition potential and optimizes intermediate binding at Ni sites, reducing the adsorbate evolution mechanism barrier. Concurrently, it induces an upshift of the O 2p band center, which activates lattice oxygen and lowers the energy barrier along the lattice oxygen mechanism pathway. Our findings highlight the synergistic optimization of the dual mechanisms, demonstrating superior catalytic performance of Si-NiFe-LDH/NF in 1 mol L^-1 KOH relative to NiFe-LDH/NF, where OER overpotentials are reduced by 24% and 14.4% at current densities of 10 and 100 mA cm^-2, respectively. In addition, a low hydrogen evolution reaction overpotential of 112 mV at 10 mA cm^-2 is achieved. Finally, we demonstrate the strong potential of our strategy in industrial applications through the operation (at 1.55 V) of an assembled solar-powered total water electrolyzer.

Key words: Silicon doping, M-O-Si bond, Rapid etching, Oxygen evolution reaction, Water electrolysis

Jing Xie, Ying Tang, Songbo Ye, Wentao Bao, Tiantian Wang, Yunxia Zhao, Shifu Wang, Jie Yu, Xuning Li, Hao Li, Feng Yu. Activating synergetic adsorbate evolution and lattice oxygen mechanisms in NiFe-LDH via M-O-Si bonding for improved oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2026, 91: 210-221.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65225-4

https://www.cjcatal.com/EN/Y2026/V91/I12/210

Figures/Tables 6

Fig. 1. (a) Schematic of SiCl4 etching for NiFe-LDH/NF nanoflowers. SEM images of NiFe-LDH/NF (b) and Si-NiFe-LDH/NF (c,d). (e,f) HRTEM images of Si-NiFe-LDH/NF. (g) Selected area electron diffraction pattern of Si-NiFe-LDH/NF. (h) EDX elemental-mapping results of Si-NiFe-LDH/NF.

Fig. 2. XRD patterns (a), FTIR spectra (b), and EPR spectra (c) of NiFe-LDH/NF and Si-NiFe-LDH/NF. XPS spectra of O 1s (d), Si 2p (e), Ni 2p (f), and Fe 2p (g). Mössbauer spectra of NiFe-LDH/NF (h) and Si-NiFe-LDH/NF (i).

Fig. 3. Electrocatalytic performance of NiFe-LDH/NF and Si-NiFe-LDH/NF in a 1 mol L-1 KOH solution: iR-corrected LSV curves for the OER (a), comparison plot of OER overpotentials (b), Tafel plots (c), EIS and equivalent-circuit-fitting plots (d), and ECSA normalized specific activities for the OER (1.48 VRHE) (e). (f) Chronopotentiometry curve of Si-NiFe-LDH/NF at different current densities. NiFe-LDH/NF and Si-NiFe-LDH/NF in a 1 mol L-1 KOH solution: iR-corrected LSV curves for the HER (g), comparison plot of HER overpotentials (h), Tafel slope (i), and EIS and equivalent-circuit-fitting plots (j). (k) Chronopotentiometry curve of Si-NiFe-LDH/NF at -15 mA cm-2.

Fig. 4. (a) Schematic illustration of the assembled two-electrode system. (b) LSV curves for overall water splitting. (c) Chronopotentiometry curve of the Si-NiFe-LDH/NF‖Si-NiFe-LDH/NF electrolyzer at different current densities. (d) Schematic of the solar energy-driven overall water-splitting system. (e) Comparison of the electrolysis voltages of Si-NiFe-LDH/NF with those of some previously reported Ni-based catalysts.

Fig. 5. In-situ Raman spectra of NiFe-LDH/NF (a) and Si-NiFe-LDH/NF (d). In-situ ATR-FTIR spectra of NiFe-LDH/NF (b) and Si-NiFe-LDH/NF (e). LSV curves of NiFe-LDH/NF (g) and Si-NiFe-LDH/NF (h) in 1 mol L-1 KOH and 1 mol L-1 TMAOH detected DEMS signals. (i) Calculated signal peak areas of O32, O34, and O36.

Fig. 6. Gibbs free-energy diagrams of NiFe-LDH/NF and Si-NiFe-LDH/NF for the OER: AEM pathway (a,b) and LOM pathway (d). (c) Microkinetic volcano model plotted for NiFe-LDH/NF and Si-NiFe-LDH/NF at a current density of 1 mA cm-2. (e) PDOS of O for NiFe-LDH/NF and Si-NiFe-LDH/NF. (f) Schematic illustration of the AEM-LOM compatible mechanism.

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