Synergistic electrode-electrolyte coupling enabled highly efficient and durable high entropy intermetallic-based electrocatalyst for oxygen reduction reaction

doi:10.1016/S1872-2067(25)64873-X

Abstract

Abstract:

Developing highly efficient and robust Pt-based electrocatalysts for oxygen reduction reaction (ORR) remains a substantial challenge due to the sluggish kinetics of proton-coupled electron transfer (PCET) process. Herein, an effective innovation strategy involves the rational construction of supported high-entropy intermetallics (HEIs) Pt₄FeCoNiSn, and its coupling with the ionic liquid [MTBD]⁺ is developed to simultaneously facilitate PCET steps of ORR. The anchoring effect of the substrate Co-NC and the induction effect of Sn atom conspicuously promote the formation of ordered Pt₄FeCoNiSn intermetallics at lower temperature. The multiple electron effects of HEIs and strong metal-support interactions enable Pt₄FeCoNiSn/CoNC with the half-wave potential (E_1/2) of 0.906 V in 0.1 mol L^-1 HClO₄ solution and 0.958 V in 0.1 mol L^-1 KOH solution, and long-term stability over 70 K cycles. Further [MTBD]⁺ modification of electrocatalyst leads to the enhancement in ORR performance, where the [MTBD]⁺ promotes the accumulation of reaction intermediates and increases the proportion of weakly hydrogen-bonded water at the electrode-electrolyte interface, thereby accelerating proton transfer rate during the ORR process. The Zn-air battery assembled by Pt₄FeCoNiSn/CoNC as oxygen electrode exhibits a high maximal power density of 190.2 mW cm^-2 at current density of 279.4 mA cm^-2, superior to those of Pt/C.

Key words: High-entropy intermetallics, Oxygen reduction reaction, Ionic liquids, Electrode-electrolyte interface, Metal-support interaction

Weiping Xiao, Yue Zhang, Na Wang, Xiaofei Yang. Synergistic electrode-electrolyte coupling enabled highly efficient and durable high entropy intermetallic-based electrocatalyst for oxygen reduction reaction[J]. Chinese Journal of Catalysis, 2026, 82: 92-104.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64873-X

https://www.cjcatal.com/EN/Y2026/V82/I3/92

Figures/Tables 6

Fig. 1. (a) The synthesis illustration of the Pt4FeCoNiSn/CoNC catalysts coupled with [MTBD]+ towards ORR. (b) XRD patterns of Pt4FeCoNiSn/CoNC, Pt3FeCoNi/CoNC and Co-NC. (c) XRD patterns of Pt4FeCoNiSn/CoNC at different temperatures. SEM (d) and TEM (e) images of Pt4FeCoNiSn/CoNC. (f, g) enlarged lattice diagrams of yellow box (A and B) in the (e). (h) The STEM image and corresponding element mappings.

Fig. 2. XPS survey spectra of Pt3FeCoNi/CoNC (a) and Pt4FeCoNiSn/CoNC (b). XPS spectra of the catalysts: Pt 4f (c), Co 2p (d), N 1s (e), and C 1s (f).

Fig. 3. ORR performances of Pt/C, Co-NC, PtSn/CoNC, Pt3FeCoNi/CoNC, Pt4FeCoNiSn/CoNC: LSV (a), MA (b), Tafel slope (c) in 0.1 mol L-1 HClO4 solution; LSV (d), MA (e), Tafel slope (f) in 0.1 mol L-1 KOH solution.

Fig. 4. ORR performances of Pt4FeCoNiSn/CoNC: LSV (a), MA (b), and Tafel slope (c) in 0.1 mol L-1 HClO4 solution and the addition of different concentrations of [MTBD]+. (d) In-situ ATR-SEIRAS spectra of Pt4FeCoNiSn/CoNC on Au electrode with [MTBD]+ during potential scan from 0.2 to 1.0 V. (e) In-situ ATR-SEIRAS spectra during reverse potential scan from 1.0 to 0.2 V. (f,g) Relative strengths of strong/weak hydrogen-bond species at potential of 0.2 and 1.0 V.

Fig. 5. CV (a), LSV (b), and MA (c) of Pt4FeCoNiSn/CoNC before and after ADT. CV (d), LSV (e), and MA (f) of Pt3FeCoNi/CoNC before and after ADT. Pt4FeCoNiSn/CoNC catalyst after 70 K potential cycles: TEM images (g) and enlarged lattice diagrams (h,i) of yellow box (A and B) in the (g).

Fig. 6. Electrochemical performance of Zn-air batteries. (a) Schematic of a rechargeable ZAB. (b) The open-circuit potential. (c) Discharge polarization curves and power density plots. (d) Discharge curves at different current densities.

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