氧空位与磷掺杂调控钴基双功能电解水催化剂

Modulation of Cobalt-Based Bifunctional Electrochemical Water Splitting Catalysts via Oxygen Vacancies and Phosphorus Doping

  • 摘要: 电解水制氢是绿氢制取的重要技术路径,已成为解决环境污染和能源危机问题的有效方法。因现有的铂碳(Pt/C)和钌铱(Ru/Ir)为代表的贵金属析氢催化剂原料稀缺,非贵金属电催化材料的研究迫在眉睫。本文以泡沫镍(NF)为基底,通过真空热处理结合磷掺杂策略,开发了高性能钴基双功能电解水催化剂(P-Ov-Co3O4/NF-Z)。结果表明:磷掺杂显著提升总氧空位含量,P-Ov-Co3O4/NF-Z展现卓越双功能活性:析氢反应(HER)在−10 mA·cm−2下过电位仅61 mV,接近Pt/C@NF的55 mV;析氧反应(OER)在10 mA·cm−2下过电位为228 mV,显著优于IrO2@NF和未掺杂样品,HER和OER的Tafel斜率分别为78.67和110.4 mV dec−1。催化剂在50、100、300 mA·cm−2电流下均表现出良好稳定性(HER 148 h, OER 192 h)。本文为非贵金属点催化材料的制备提供了新的思路和策略。

     

    Abstract: Electrochemical water splitting for hydrogen production is a crucial technological pathway for obtaining green hydrogen and has emerged as an effective method to address environmental pollution and the energy crisis. However, the scarcity of raw materials for noble metal hydrogen evolution catalysts, such as platinum-carbon (Pt/C) and ruthenium/iridium (Ru/Ir), makes the development of non-precious metal electrocatalytic materials an urgent priority.This study developed a high-performance cobalt-based bifunctional water electrolysis catalyst (P-Ov-Co3O4/NF-Z) using nickel foam (NF) as a substrate, through a strategy combining vacuum heat treatment and phosphorus doping. The results indicate that phosphorus doping significantly increases the total oxygen vacancy content. The P-Ov-Co3O4/NF-Z catalyst exhibits remarkable bifunctional activity: for the hydrogen evolution reaction (HER), it requires an overpotential of only 61 mV at a current density of −10 mA·cm−2, which is close to the 55 mV required by the Pt/C@NF benchmark. For the oxygen evolution reaction (OER), the overpotential is 228 mV at 10 mA·cm−2, significantly outperforming IrO2@NF and the undoped sample. The Tafel slopes for HER and OER are 78.67 mV·dec−1 and 110.4 mV·dec−1, respectively. Furthermore, the catalyst demonstrates excellent stability at current densities of 50, 100, and 300 mA·cm−2, maintaining performance for 148 hours (HER) and 192 hours (OER).This work provides new insights and strategies for the preparation of non-precious metal electrocatalytic materials.

     

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