电极-电解质协同耦合实现高熵金属间化合物电催化剂的高效稳定氧还原性能

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

摘要/Abstract

摘要：

燃料电池与锌-空气电池作为新兴能源转换技术, 具有环境友好、可持续再生且能量转换效率高等优点; 但其功率密度与长期稳定性受制于缓慢的氧还原反应(ORR). 目前, 铂(Pt)基材料因其独特的电子结构和适中的含氧物种结合能, 被视为最优异的ORR催化剂. 然而, 纯铂催化剂在长期循环过程中易发生颗粒团聚, 导致活性衰减. 构筑高熵金属间化合物(HEIs)可以凭借长程有序的原子排列和固有的高熵效应提升结构稳定性, 并通过多电子耦合效应加快ORR电子转移速率, 从而提升催化性能. 然而ORR的机理不仅涉及电极表面的电子转移, 还涉及电极-电解质界面的质子转移. 因此, 基于电极-电解质耦合设计高效ORR催化剂, 并揭示电子/质子协同转移机制至关重要.

离子液体(如吡啶阳离子)中的氮原子可以与电解质水溶液中的氢离子形成氢键, 破坏氢键水网络的形成, 从而调控界面质子转移速率. 本研究提出一种电极-电解质耦合策略: 通过合理构建负载型HEIs, 并耦合离子液体, 同步优化ORR反应的电子和质子转移速率, 促进质子耦合电子转移过程. 基于电子金属-载体相互作用, 利用具有丰富锚定位点的Co-NC载体锚定Pt、Fe、Co、Ni及Sn原子, 构建负载型HEIs Pt₄FeCoNiSn/CoNC. 引入低熔点Sn原子可促进催化剂从无序结构向有序结构转变, 从而在较低温度(500 ^oC)下成功制备出平均粒径为2.34 nm的Pt₄FeCoNiSn/CoNC复合材料. 高熵合金的多电子效应与强金属-载体相互作用使得复合电催化剂展示出优异的ORR活性: 在0.1 mol L⁻¹ HClO₄溶液中, 半波电位(E_1/2)达0.906 V; 在0.1 mol L⁻¹ KOH溶液中, E_1/2高达0.958 V. 复合电催化剂同时表现出优异的稳定性, 在0.1 mol L⁻¹ HClO₄溶液中经过70000次循环伏安衰减测试后, E_1/2仅下降6 mV. 为进一步提升ORR性能, 将Pt₄FeCoNiSn/CoNC与离子液体[MTBD]⁺耦合, 协同促进反应过程中的质子耦合电子转移速率. 原位衰减全反射表面增强红外吸收光谱结果表明, [MTBD]⁺修饰后, 催化剂通过促进反应中间体富集、增加电极-电解质界面弱氢键水分子比例, 显著加速质子传输速率, 从而使得Pt₄FeCoNiSn/CoNC+0.1 mmol L⁻¹ [MTBD]⁺在0.1 mol L⁻¹ HClO₄中的E_1/2提升约42 mV. 以Pt₄FeCoNiSn/CoNC催化剂为氧电极组装的锌空气电池, 在电流密度279.4 mA cm^-2时, 最大功率密度达190.2 mW cm^-2, 该性能优于商业Pt/C电催化剂组装的电池.

综上, 本工作基于电极-电解质耦合策略构筑的新型高熵金属间化合物@离子液体复合体系, 协同促进了氧还原反应过程中的电子和质子转移, 获得了高效稳定的电催化性能, 弥补了单一催化剂在质子耦合电子转移过程中的不足, 为设计高性能ORR电催化剂提供了新思路.

关键词: 高熵金属间化合物, 氧还原反应, 离子液体, 电极-电解质界面, 金属-载体相互作用

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

肖卫平, 张跃, 王娜, 杨小飞. 电极-电解质协同耦合实现高熵金属间化合物电催化剂的高效稳定氧还原性能[J]. 催化学报, 2026, 82: 92-104.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64873-X

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

图/表 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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