High entropy engineering promoted active sites in layered double hydroxide for seawater oxygen evolution reaction

doi:10.1016/S1872-2067(26)65180-7

Abstract

Abstract:

Efficient oxygen-evolving electrodes that can operate under high-current-density alkaline water/seawater electrolysis are essential for practical hydrogen production, yet the simultaneous achievement of high activity, chloride tolerance, and long-term durability remains difficult for non-precious-metal catalysts. In this work, a binder-free high-entropy layered double hydroxide electrode has been successfully constructed by directly growing multimetal LDH nanosheets on nickel foam through a facile one-step hydrothermal process. The optimized quinary LDH, composed of five non-noble transition metals, namely Fe, Ni, Co, Zn, and Cr, is denoted as CoNiFeZnCr LDH@NF. Benefiting from the high-entropy multimetal coordination environment, this electrode exhibits superior OER performance compared with the corresponding binary, ternary, and quaternary LDH counterparts. In alkaline seawater, CoNiFeZnCr LDH@NF requires a low OER overpotential of 250 mV to reach 100 mA cm^-2 and shows a Tafel slope of 66.93 mV dec^-1. The electrode also maintains stable operation for 200 h at 100 mA cm^-2, indicating strong resistance to seawater-induced degradation. Density functional theory calculations further reveal that the quinary high-entropy configuration optimizes the adsorption behavior of *O intermediates and lowers the energy barrier of the rate-determining OER step. The improved activity and durability are therefore attributed to the synergistic electronic and structural effects arising from the incorporation of Fe, Ni, Co, Zn, and Cr into the LDH framework. This study demonstrates a practical high-entropy engineering strategy for developing robust non-precious-metal OER electrodes toward seawater-relevant hydrogen production.

Key words: Layered double hydroxide, High entropy engineering, Seawater oxygen evolution reaction, Alkaline seawater electrolysis, Non-precious-metal catalyst

Peiran Chen, Luo Cheng, Congbao Guo, Yu He, Yangyang Liu, Yi Wang, Shuqin Song. High entropy engineering promoted active sites in layered double hydroxide for seawater oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2026, 89: 246-257.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65180-7

https://www.cjcatal.com/EN/Y2026/V89/I10/246

Figures/Tables 6

Fig. 1. (a) Schematic illustration for the preparation of CoNiFeZnCr LDH@NF. (b) XRD patterns of LDHs. SEM image (c), TEM image with SAED patterns and HRTEM image (d) (inset: the corresponding lattice fringe pattern) of the CoNiFeZnCr LDH@NF. (e-k) HAADF-STEM image of CoNiFeZnCr LDH@NF and element mappings of CoNiFeZnCr LDH for Ni (green), Fe (yellow), Co (orange), Zn (purple), Cr (indigo), and O (red).

Fig. 2. High-resolution XPS spectra of LDH electrodes. Spectra were collected for CoNiFeZnCr LDH@NF, CoNiFeZn LDH@NF, CoNiFe LDH@NF, and NiFe LDH@NF unless otherwise specified. (a) Ni 2p; (b) Fe 2p; (c) Co 2p (Co-containing samples); (d) Zn 2p (CoNiFeZnCr LDH@NF and CoNiFeZn LDH@NF); (e) Cr 2p (CoNiFeZnCr LDH@NF); (f) O 1s.

Fig. 3. Electrocatalytic performances of the different catalysts in 1.0 mol L-1 KOH solution. (a) LSV curves. (b) Comparison of overpotential and the corresponding current density with the reported data, which detailed information can be found in Table S4. (c) Tafel plots. (d) EIS at a potential of 1.456 V (vs. RHE). (e) ECSA. (f) LSV curves normalized by ECSA.

Fig. 4. LSV curves (a) and EIS (b) of the different catalysts in 1.0 mol L-1 KOH + seawater solution. (c) LSV curves of CoNiFeZnCr LDH@NF in different electrolytes. (d) Overpotentials at 100 and 500 mA cm-2 from polarization curves presented in (c). (e) Measured (dots), theoretical (solid lines) gaseous products, and Faradaic efficiency of CoNiFeZnCr LDH@NF at 500 mA cm-2 in alkaline simulated seawater (1.0 mol L-1 KOH + 0.5 mol L-1 NaCl). (f) LSV curves of CoNiFeZnCr LDH@NF before and after 200 h chronopotentiometry stability test in 1.0 mol L-1 KOH + seawater electrolyte. (g) Stability test with chronopotentiometry on CoNiFeZnCr LDH@NF and NiFe LDH@NF at 100 mA cm-2.

Fig. 5. Overall alkaline simulated seawater electrolysis. (a) Schematic diagram of AWE. (b) LSV curves for the CoNiFeZnCr LDH@NF||Pt/C@NF, CoNiFeZn LDH@NF||Pt/C@NF, and CoNiFe LDH@NF||Pt/C@NF, and NiFe LDH@NF||Pt/C@NF. (c) EIS of CoNiFeZnCr LDH@NF||Pt/C@NF, CoNiFeZn LDH@NF||Pt/C@NF, and CoNiFe LDH@NF||Pt/C@NF, and NiFe LDH@NF||Pt/C@NF. (d) Stability test with chronopotentiometry on CoNiFeZnCr LDH@NF||Pt/C@NF and NiFe LDH@NF||Pt/C@NF at 500 mA cm-2.

Fig. 6. (a) Schematic illustration of the four-step OER process on the surface of the CoNiFeZnCr LDH catalyst. (b) Gibbs free-energy diagram of O-containing intermediates. (c) Calculated DOS for Co, Ni, Fe, Zn, and Cr in CoNiFeZnCr LDH, with the Fermi level indicated by the black dashed line. (d) d-band centers of CoNiFeZnCr LDH, CoNiFeZn LDH, CoNiFe LDH, and NiFe LDH.

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