物理化学学报

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基于MOF-on-MOF核壳结构的Co@Fe纳米复合材料的制备及其超宽带微波吸收性能

司元靖1, 胡玉鹏1, 卢茂霞1, 马东威2, 宋安敏1, 张道海1   

  1. 1 贵州民族大学化学工程学院, 贵州 贵阳 550025;
    2 湖北汽车工业学院汽车材料学院, 湖北 十堰 442002
  • 收稿日期:2026-06-22 修回日期:2026-07-27 录用日期:2026-08-13
  • 通讯作者: 宋安敏, 张道海 E-mail:songanmin0919@163.com;zhangdaohai6235@163.com
  • 基金资助:
    本研究得到了国家自然科学基金项目(52163001)、贵州省科技计划项目(黔科合平台人才-GCC[2022]010-2、黔科合中引地[2024]042、黔科合基础-ZK[2024]YB488、黔科合中引地(2025)013、黔科合成果[2025]109、黔科合人才XKBF (2025)005)、贵州省科学家工作站(黔科合平台KXJZ[2024]022)以及贵阳市白云区科技计划项目(白科合[2025]3、白科合[2025]4)的资助。

Preparation of Co@Fe nanocomposites based on a MOF-on-MOF Core-shell structure and their Ultra-Broadband microwave absorption properties

Yuanjing Si1, Yupeng Hu1, Maoxia Lu1, Dongwei Ma2, Anmin Song1, Daohai Zhang1   

  1. 1 School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, Guizhou Province, China;
    2 School of Automotive Materials, Hubei University of Automotive Technology, Shiyan 442002, Hubei Province, China
  • Received:2026-06-22 Revised:2026-07-27 Accepted:2026-08-13
  • Contact: Anmin Song, Daohai Zhang E-mail:songanmin0919@163.com;zhangdaohai6235@163.com

摘要: 开发宽带、高性能微波吸收材料对于电磁污染控制和先进隐身技术具有迫切需求。基于MOF-on-MOF策略构建的核壳结构可形成丰富异质界面,为精确调控磁损耗与介电损耗提供了前所未有的机遇,从而能够合理设计高效微波吸收材料。尽管MOF衍生微波吸收体已取得显著进展,但若干固有瓶颈仍制约其实际应用。传统单MOF衍生磁性碳材料通常缺乏足够异质界面,导致难以协同调控介电损耗与磁损耗。更值得注意的是,当前最先进的MOF基吸收体普遍面临有效吸收带宽与匹配厚度之间不可调和的权衡困境。为获得宽有效吸收带宽,多数已报道吸收体需要超过2.5 mm的厚涂层,这无法满足隐身与电磁兼容设备对超薄轻质的要求。此外,单金属MOF前驱体在热解过程中缺乏双金属离子互扩散的天然通道,限制了多级异质界面的构建以诱发强界面极化弛豫。针对上述局限,我们报道了一种新型MOF-on-MOF方法,将Fe基MIL-88A原位生长于Co-BTC表面,成功构建了Co-BTC@MIL-88A核壳前驱体。随后通过600 °C-900 °C梯度热解制备了一系列Co@Fe纳米复合材料。值得注意的是,在800 °C热解样品(CM8)在2-18 GHz范围内,仅需2.31 mm超薄匹配厚度即可实现6.99 GHz的优异有效吸收带宽,完全覆盖整个C波段和X波段。其卓越的微波吸收性能源于三个协同因素:(i) 核壳结构产生的丰富界面极化效应;(ii) Co-Fe合金化诱导的显著磁损耗能力;(iii) 磁损耗与介电损耗之间优化的阻抗匹配与互补协同作用。

关键词: 核壳结构, Co@Fe纳米复合材料, 微波吸收, 界面极化

Abstract: The development of broadband, high-performance microwave absorption materials (MAMs) is urgently demanded for both electromagnetic pollution control and advanced stealth technology. The MOF-on-MOF strategy, which constructs rich heterogeneous interfaces through core-shell architecture, offers unprecedented opportunities for precisely tuning magnetic and dielectric losses, thereby enabling the rational design of high-efficiency MAMs. Despite the promising achievements of MOF-derived microwave absorbers, several inherent bottlenecks still hinder their practical implementation. Traditional single-MOF derived magnetic carbon materials usually lack sufficient heterogeneous interfaces, leading to difficulties in synergistically modulating dielectric loss and magnetic loss. More notably, state-of-the-art MOF-based absorbers generally face an unavoidable trade-off dilemma between effective absorption bandwidth and matching thickness. To obtain wide effective absorption bandwidth, most reported absorbers demand thick layers over 2.5 mm, which fails to satisfy the ultrathin and lightweight requirements for stealth and electromagnetic compatibility equipment. Moreover, single-metal MOF precursors lack natural channels for bimetallic ion interdiffusion during pyrolysis, which restricts the creation of abundant multi-level heterointerfaces to induce strong interfacial polarization relaxation. To address the above limitations, we report a novel MOF-on-MOF approach wherein Fe-based MIL-88A is in-situ grown onto Co-BTC surfaces, successfully constructing a Co-BTC@MIL-88A core-shell precursor. A series of Co@Fe nanocomposites are subsequently prepared via gradient pyrolysis at 600 °C-900 °C. Notably, the sample pyrolyzed at 800 °C (CM8) achieves an exceptional effective absorption bandwidth (EAB) of 6.99 GHz at an ultra-thin matching thickness of only 2.31 mm in the 2-18 GHz range, fully covering the entire C-band and X-band.. The outstanding microwave absorption performance originates from three synergistic factors: (i) abundant interfacial polarization effects arising from the core-shell architecture; (ii) pronounced magnetic loss capacity induced by Co-Fe alloying; and (iii) optimized impedance matching and complementary synergy between magnetic and dielectric losses.

Key words: Core-shell structure, Co@Fe nanocomposites, Microwave absorption, Interfacial polarization