催化学报

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铈活化泡沫金属载体实现高效乙酸丁酯氧化: 内在氧化还原循环与界面电子转移的双重作用

邢赟a, 刘磊a, 孔文晶a, 田俊泰a, 刘鹏a, 杨臣a, 付名利a,b,*, 叶代启a,b   

  1. a华南理工大学环境与能源学院, 广东广州 510006;
    b广东省大气环境与污染控制重点实验室, 广东广州 510006
  • 收稿日期:2025-09-12 接受日期:2025-09-12
  • 通讯作者: * 电子信箱: mlfu@scut.edu.cn (付名利).
  • 基金资助:
    移动源排放控制技术国家工程实验室(NELMS2020A06); 中央高校基本科研业务费专项资金(2023ZYGXZR058).

Ce-activated metallic foam carriers for efficient butyl acetate oxidation: Dual roles of intrinsic redox cycling and interfacial electron transfer

Yun Xinga, Lei Liua, Wen-Jing Konga, Jun-Tai Tiana, Peng Liua, Chen Yanga, Ming-Li Fua,b,*, Dai-Qi Yea,b   

  1. aSchool of Environment and Energy, South China University of Technology, Guangzhou 510006, Guangdong, China;
    bGuangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, Guangzhou 510006, Guangdong, China
  • Received:2025-09-12 Accepted:2025-09-12
  • Contact: * E-mail: mlfu@scut.edu.cn (M.-L. Fu).
  • Supported by:
    National Engineering Laboratory for Mobile Source Emission Control Technology (NELMS2020A06) and the Fundamental Research Funds for the Central Universities (2023ZYGXZR058).

摘要: 含氧挥发性有机化合物(OVOCs), 以乙酸丁酯为代表, 因其低气味阈值、广泛的工业排放源及其对生态系统和人体健康的有害影响, 已成为严峻的大气污染问题. 高效净化OVOCs不仅是改善区域空气质量的关键, 也符合绿色化学通过减少有害物排放与过程能耗以实现可持续生产的核心原则. 因此, 开发高效、稳定的催化净化技术, 对缓解OVOCs对环境和公众健康的威胁具有迫切现实意义.
本研究旨在开发一种兼具高活性与优异稳定性的整体式催化剂, 以应对实际应用中乙酸丁酯的催化去除挑战. 创新性地采用原位生长法, 将活性组分Ce直接构筑于三维多孔的Co-Ni合金泡沫载体上, 成功合成了Ce/Co-Ni泡沫整体催化剂. 该设计策略不仅实现了活性组分的高效负载, 更关键的是, Ce元素的引入发挥了多重协同催化效应. CeO2固有的高氧储存能力显著提升了催化体系的氧化还原性能, 促进了反应物分子的活化与深度氧化. 深入的表征与机理研究表明, Ce物种能够有效激活泡沫载体表面的Co-Ni合金, 促进金属载体间的电子转移, 从而协同加速了Ce4+/Ce3+, Co3+/Co2+及Ni2+/Ni3+多个氧化还原对的循环. 这一过程持续诱导产生大量表面氧空位, 为氧化反应提供了丰富的活性位点. 性能测试结果表明, 所制Ce/Co-Ni泡沫催化剂在230 °C对乙酸丁酯的去除效率超过99%. 尤为重要的是, 催化剂展现出卓越的实际应用潜力: 在长达48 h的长期稳定性测试中, 其活性未见明显衰减; 即使在湿度(H2O)高达8 vol%的严苛条件下, 去除效率仍能维持80%以上, 表现出较好的抗水性能. 本研究进一步揭示, 三维泡沫载体不仅充当物理支撑体, 更作为直接的催化活性组成部分参与反应, 这一认识对理解整体催化剂的构效关系至关重要.
综上, 本文不仅证实了所设计的Ce/Co-Ni泡沫催化剂在OVOCs高效净化方面的优异性能与稳定性, 更通过阐明金属-载体强相互作用及多氧化还原循环协同的机理, 为未来设计面向实际复杂环境的高性能、低成本整体式催化剂提供了新颖的设计思路与坚实的理论依据.

关键词: 含氧挥发性有机污染物, 整体催化剂, CeO2物种, 电子转移, 氧空位

Abstract: Oxygenated volatile organic compounds (OVOCs) exemplified by butyl acetate, which posed severe environmental and health risks due to their low odor threshold, substantial industrial emissions, and detrimental ecological effects. The efficient abatement of OVOCs was not only imperative for air quality improvement but also aligned with the core principles of green chemistry by minimizing the release of hazardous volatiles and reducing energy consumption. There was an urgent need to develop highly efficient catalytic technologies to mitigate the persistent threat these compounds present to atmospheric environments and public health. In this study, cerium (Ce)-based monolithic catalysts synthesized by in situ growth method were developed for practical catalytic applications and demonstrated enhanced active species loading capacity. The introduction of Ce leveraged the inherent high oxygen storage capacity of CeO2 to enhance reactant activation and oxidation. Meanwhile, Ce species activate the alloy on the metallic foam support, facilitating electron transfer and promoting redox cycles between Ce4+/Ce3+, Co3+/Co2+, and Ni2+/Ni3+. This process concurrently induced additional oxygen vacancies formation. Thus, the Ce/Co-Ni foam catalyst exhibited exceptional removal efficiency exceeding 99% at 230 °C. Furthermore, it maintained removal performance above 80% under challenging conditions, including prolonged operation and the presence of 8 vol% H2O. This study revealed that the foam substrate within the monolithic catalyst served not only as structural support but also functioned as an active component, significantly influencing the overall catalytic activity. These findings provided a novel strategy for designing high-performance monolithic foam catalysts.

Key words: Oxygenated volatile organic, compounds, Monolithic catalyst, CeO2 species, Electron transfer, Oxygen vacancy