Local-atomic environment engineering of Ni-sites for industrial hydrogen production from seawater

doi:10.1016/S1872-2067(26)65051-6

Abstract

Abstract:

Seawater electrolysis integrated with renewable energy sources represents a green and sustainable pathway for hydrogen production, yet its practical application is severely constrained by the lack of cost-effective, highly active, and scalable electrodes. Herein, we report the construction of a high-performance hydrogen evolution reaction (HER) electrode by engineering the local-atomic environment of Ni sites through vanadium oxide modification. This optimized electrode delivers current densities of 500/1000 mA cm^-2 at only 283/361 mV in alkaline seawater. Impressively, a kW-scale alkaline seawater electrolyzer achieves continuous operation at an industrial-level current up to 25 A for over 880 h with an ultra-low degradation rate of 34.1 μV h^-1. Combined experimental and theoretical investigations reveal a volcano-type relationship between the chemical state of Ni and the adsorption energy of the key intermediate H* (∆G_H_*), as well as the potential of zero charge (PZC) of the electrode. Furthermore, in-situ Fourier-transform infrared spectroscopy confirms that a lower PZC promotes the formation of more free water molecules near the electrode surface, thereby facilitating the HER process. This work uncovers atomic environment-governed HER mechanisms and develops a scalable, industrially stable seawater electrolysis electrode, bridging lab-innovation to practical hydrogen production.

Key words: Local-atomic environment, Ni-sites, Hydrogen evolution, Interfacial water, Potential of zero charge

Pengfei Wu, Zhihao Lou, Yuanshuo Ma, Pengfei Wang, Da Xue, Fangyi Ma, Xuejing Cui, Guangbo Liu, Xin Zhou, Erdong Wang, Luhua Jiang. Local-atomic environment engineering of Ni-sites for industrial hydrogen production from seawater[J]. Chinese Journal of Catalysis, 2026, 87: 254-268.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65051-6

https://www.cjcatal.com/EN/Y2026/V87/I8/254

Figures/Tables 7

Fig. 1. Synthesis and structure characterizations. (a) Schematic process for synthesizing Ni/VOx. SEM (b), TEM (c) and HRTEM (d) images of Ni/V2O3 catalyst. (e) HAADF image and EDS elemental mappings of Ni/V2O3 catalyst.

Fig. 2. Chemical state and electronic structure characterizations. High resolution XPS spectra of Ni 2p (a), V 2p (b), and O 1s (c) for NF@Ni, Ni/V2O3, Ni/VO2 and Ni/V2O5. XANES spectra of the Ni K-edge (d) and average valence state (e) of Ni in Ni/V2O3, Ni/VO2 and Ni/V2O5. EXAFS spectra of the Ni K-edge (f) and wavelet-transform plots (g) for the Ni, NiO, Ni/V2O3, Ni/VO2 and Ni/V2O5.

Fig. 3. Electrocatalytic HER performances. Polarization curves (a), overpotentials at 500 and 1000 mA cm-2 (b), and Tafel curves (c) of NF@Ni, Ni/V2O3, Ni/VO2 and Ni/V2O5 in 1 mol L?1 KOH. Polarization curves (d), overpotentials at 500 and 1000 mA cm-2 (e), and Tafel curves (f) of NF@Ni, Ni/V2O3, Ni/VO2 and Ni/V2O5 in 1 mol L?1 KOH + seawater. Comparison of overpotentials at 100 mA cm-2 (η100) and Tafel slopes between Ni/V2O3 and reported catalysts in 1 mol L?1 KOH (g) and 1 mol L?1 KOH + seawater (h). (i) Chronopotentiometry curves of NF@Ni, Ni/V2O3, Ni/VO2 and Ni/V2O5 electrodes in 1 mol L?1 KOH and 1 mol L?1 KOH + seawater.

Fig. 4. In-situ impedance and interfacial water behavior. Bode plots of the in-situ electrochemical impedance spectra of NF@Ni (a), Ni/V2O3 (b), Ni/VO2 (c), and Ni/V2O5 (d) in 1 mol L-1 KOH. In-situ FTIR contour plots and spectra of interfacial water at surface of NF@Ni (e,i), Ni/V2O3 (f,j), Ni/VO2 (g,k), and Ni/V2O5 (h,l) under different potentials in 0.1 mol L-1 KOH. The proportion of 2-HB·H2O (m), 4-HB·H2O (n) and free-H2O (o) on surface of NF@Ni, Ni/V2O3, Ni/VO2 and Ni/V2O5. (p) PZC values of NF@Ni, Ni/V2O3, Ni/VO2, and Ni/V2O5.

Fig. 5. DFT calculations. (a) The structure and differential charge density of Ni/V2O3, Ni/VO2 and Ni/V2O5. (b) Partial density of state analysis and d-band centers for Ni, Ni/V2O3, Ni/VO2, and Ni/V2O5. (c) Calculated adsorption energy of H2O* (EH2O*) and OH* (EOH*) on Ni, Ni/V2O3, Ni/VO2 and Ni/V2O5. (d) Calculated hydrogen adsorption free energy on the Ni, Ni/V2O3, Ni/VO2, and Ni/V2O5. (e) Alkaline HER process on Ni/V2O3. (f) Schematic illustration of the interfacial water structure and HER process on Ni/V2O3 in seawater. (g) Relationships among calculated ΔGH*, PZC values, Ni valence, conversion rate of free-H2O, and overpotentials at 500 mA cm?2 for Ni, Ni/V2O3, Ni/VO2, and Ni/V2O5.

Fig. 6. Large-area Ni/V2O3 electrode production and uniformity characterizations. (a) Optical image of the Ni/V2O3 electrode with a geometric area of approximately 50 cm2. (b?h) SEM images of Ni/V2O3 in the selected regions in (a). LSV curves and corresponding overpotentials for the HER of the selected region of Ni/V2O3 in alkaline freshwater (i,l), alkaline seawater (j,m), and natural seawater (k,n).

Fig. 7. Performances of the kW-scale three-cell ASWE stack with Ni/V2O3 || NiFe-LDH electrodes. (a) Component and structure of one ASWE cell. (b, c) Digital images of the three-cell ASWE stack. Polarization curve (d) and Nyquist plot (e) of the three-cell ASWE stack in 6 mol L-1 KOH + seawater at 60 °C. (f) Durability and energy consumption of the three-cell ASWE stack at 25 A (0.5 A cm-2) in 6 mol L-1 KOH + seawater at 60 °C.

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