In situ SO42- regulation of ZrFeCoNiAl-based high-entropy electrocatalysts to enhance O-O coupling in the oxygen evolution reaction

doi:10.1016/j.jmst.2025.01.061

Abstract

Abstract: To overcome the sluggish kinetics and excessive overpotentials of the oxygen evolution reaction (OER), there is an imperative need for the development of highly efficient, cost-effective, and durable electrocatalysts. This study presents for the first time a strategy for in situ SO₄^2- regulation of HEMs. Unlike previous studies SO₄^2- is directly anchored to HEMs rather than formed through uncontrolled transformation or surface reconstruction. A series of novel electrocatalysts N@(ZrFeCoNiAl)O_x-SO₄ [HE/NS-(0-4)] were prepared by the low-temperature NaBH₄ reduction method. The content of SO₄^2- showed an inverse volcano relationship with the OER catalytic activity, all the samples exhibit excellent OER activity and remarkable stability over 50 h. The moderate introduction of SO₄^2--oriented HE/NS-2 forms a short-range ordered and long-range disordered structure, which stably combines high catalytic activity and excellent electrical conductivity, exhibiting LOM-dominated OER mechanism with an overpotential of 257 mV at 10 mA cm^-2 and a Tafel slope of 41.86 mV dec^-1. The catalytic performance of the highly crystalline HE/NS-4 electrode (291 mV @10 mA cm^-2) containing a large amount of SO₄^2- and the HE/NS-0 (340 mV @10 mA cm^-2) without SO₄^2- is both poor. SO₄^2- as the main promoting factor, controlling the growth of HEMs morphology, structural evolution, and the adjustment of the valence state of active metal sites, playing a vital role in activating lattice oxygen and promoting O-O coupling. N as an electron donor, further improves the electronic structure of HEMs. In situ Raman spectroscopy to probe the dynamic reconstruction of HE/NS-2, anion/cation leaching facilitates self-reconstruction, and the formed metal (oxy)hydroxide is considered the active center of OER. This study pioneers a novel avenue for the controlled synthesis of oxidized anion-adsorbed HEMs and enhancing OER catalytic activity.

Key words: In situ SO₄^2- regulation, Short-range order and long-range disorder structure, Phase evolution, Activation of lattice oxygen, Zr-HEMs, Surface reconstruction

Bingxuan Zhai, Yan He, Jiawen Chen, Xuemin Cui, Leping Liu. In situ SO₄^2- regulation of ZrFeCoNiAl-based high-entropy electrocatalysts to enhance O-O coupling in the oxygen evolution reaction[J]. J. Mater. Sci. Technol., 2025, 234: 151-163.

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In situ SO₄^2- regulation of ZrFeCoNiAl-based high-entropy electrocatalysts to enhance O-O coupling in the oxygen evolution reaction

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