碳纳米管协同高熵钙钛矿氟化物增强碱性电催化析氧性能及机制

Synergistic Effect of Carbon Nanotubes and High-entropy Perovskite Fluorides for Enhanced Alkaline Oxygen Evolution Performance and Mechanism

摘要

采用一锅溶剂热法, 使聚乙烯吡咯烷酮(PVP)修饰的高熵钙钛矿氟化物(HEPF)组分在预先分散的多壁碳纳米管(CNTs)表面原位成核、 生长并锚定, 构筑了具有三维交织网络的 HEPF-PVP/CNT 复合电催化剂. CNTs作为异相成核支架, 实现了HEPF纳米颗粒的均匀锚定与高度分散, 有效克服了纯相高熵氟化物易团聚和导电性差的缺陷. 微观表征表明, 适量碳骨架(CNT-20)的引入发挥了空间限域作用, 显著提升了比表面积与活性位点暴露程度; 同时, 异质界面产生强电子耦合效应, 诱导金属中心电子云重新分布, 提升了Co³⁺和Fe³⁺等高价活性位点比例, 抑制了易溶出Cr⁶⁺的生成. 电化学测试显示, 最优HEPF-PVP/CNT-20催化剂在10 mA/cm²电流密度下的过电位仅为258 mV, Tafel斜率为85 mV/dec, 连续运行120 h后过电位仅增加10.7 mV, 表现出优异的长期稳定性. 本研究为设计高活性、 长寿命的多金属协同电催化网络提供了可靠的结构工程策略.

Abstract

In this work, a HEPF-PVP/CNT composite electrocatalyst with a three-dimensional interwoven network was successfully constructed by anchoring polyvinylpyrrolidone (PVP)-modified high-entropy perovskite fluoride (HEPF) nanoparticles onto pre-dispersed multi-walled carbon nanotubes (CNTs) via an in-situ nucleation and growth process during a one-pot solvothermal reaction. Serving as heterogeneous nucleation scaffolds, CNTs achieved uniform anchoring and high dispersion of HEPF nanoparticles, effectively overcoming the inherent defects of severe agglomeration and poor conductivity in pristine high-entropy fluorides. Microscopic characterizations revealed that the introduction of an optimal carbon skeleton (CNT-20) exerted a spatial confinement effect, significantly increasing the specific surface area and the exposure degree of active sites. Meanwhile, strong electronic coupling effects emerged at the hetero-interface, inducing the redistribution of electron clouds at metal centers, which increased the proportion of high-valence active sites such as Co³⁺ and Fe³⁺, and suppressed the generation of easily leachable Cr⁶⁺. Electrochemical tests demonstrated that the optimal HEPF-PVP/CNT-20 catalyst delivered a low overpotential of only 258 mV at a current density of 10 mA/cm², with a Tafel slope of 85 mV/dec, and showed only a 10.7 mV increase in overpotential after 120 h of continuous operation. This work provides a reliable structural engineering strategy for designing multi-metal synergistic electrocatalytic networks with high activity and long lifespan.

关键词

高熵钙钛矿氟化物 / 碳纳米管 / 析氧反应 / 界面电子耦合 / 原位合成

Key words

High-entropy perovskite fluorides / Carbon nanotubes / Oxygen evolution reaction / Interfacial electronic coupling / In-situ synthesis

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基金资助

吉林省科技厅重点研发计划国际科技合作项目(20260205046GH)