有机物包覆磁铁矿纳米颗粒的团聚行为及稳定性机制研究进展

Research Progress on the Aggregation Behavior and Stability Mechanisms of Organic-Coated Magnetite Nanoparticles

  • 摘要: 磁铁矿纳米颗粒(MNPs)因比表面积大、反应活性强及磁性分离便捷,被广泛应用于重金属吸附、有机污染物降解和水体修复。然而,MNPs在水环境中易发生团聚,导致比表面积与活性位点减少、迁移性降低,从而限制其修复效率。表面包覆有机物是提升MNPs胶体稳定性的重要策略,但包覆类型多样、环境因子作用复杂,其调控机制尚需系统归纳。本文综述了小分子有机酸、高分子聚合物与表面活性剂对MNPs稳定性的影响规律。小分子有机酸,如乙酸(AA)、柠檬酸(CA)、油酸(OA)等,主要通过–COOH/–OH官能团调节表面电荷,可将zeta电位(ζ)由约–20 mV降至–30~–35 mV,从而提升静电排斥力;高分子聚合物,如聚丙烯酸(PAA)、聚乙二醇(PEG)、羧甲基纤维素(CMC)等,形成厚度5~20 nm的空间位阻层,使ζ的绝对值(|ζ|)维持在30~40 mV,并在高盐、宽pH范围内保持良好分散性。其中,CMC-MNPs的水合直径稳定在40~120 nm,对Pb2+的吸附量达152 mg/g,表现出优异的环境适应性。环境pH、离子强度、离子价态及天然有机质(NOM)是影响有机物包覆的MNPs稳定性的主控因子,其中NOM在MNPs表面的吸附量是有机物吸附量的50~250倍,可重塑表面化学性质并影响团聚机制。此外,光照、氧化、老化与微生物过程亦可破坏或重构包覆层,使团聚机制在“抑制–促进”之间切换。基于DLVO/EDLVO理论及动态光散射(DLS)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等分析测试手段的研究表明,MNPs的团聚由静电排斥、空间位阻、阳离子键桥作用、补丁电荷吸引等多力耦合控制,并随环境条件发生主导机制转变。深入理解有机包覆与环境因子的协同调控机制,可为构建高稳定性、环境友好的MNPs修复材料提供理论依据。

     

    Abstract: Magnetite nanoparticles (MNPs) have been widely used for heavy metal adsorption, organic pollutant degradation and water remediation owing to their large specific surface area, high reactivity and facile magnetic separation. However, pristine MNPs readily aggregate in aquatic environments, which reduces accessible surface area and active sites, lowers mobility, and ultimately limits remediation efficiency. Surface organic coating is an effective strategy to enhance the colloidal stability of MNPs, yet the diversity of coating types and the complexity of environmental factors make the underlying regulation mechanisms insufficiently clarified. This review summarizes the effects of small organic acids, polymeric ligands and surfactants on the stability of MNPs. Small organic acids such as acetic acid (AA), citric acid (CA) and oleic acid (OA) regulate surface charge via –COOH/–OH groups, typically shifting the zeta potential from about −20 mV to −30 – −35 mV and thus strengthening electrostatic repulsion. Polymeric coatings such as poly(acrylic acid) (PAA), polyethylene glycol (PEG) and carboxymethyl cellulose (CMC) form 5–20 nm steric layers, maintain |ζ| at 30–40 mV, and ensure good dispersion under high salinity and over a broad pH range. For example, CMC-coated MNPs exhibit hydrodynamic diameters of 40–120 nm and a Pb2+ adsorption capacity of 152 mg/g, indicating excellent environmental robustness. Environmental pH, ionic strength, ion valence, and natural organic matter (NOM) are identified as primary controls on organic coated MNPs stability; NOM adsorption, typically 50–250 times higher than that of the original organic coating, can reconfigure surface chemistry and aggregation pathways. In addition, light, oxidative ageing and microbial processes may destroy or reconstruct coatings, switching aggregation mechanisms between suppression and promotion. Evidence from DLVO/EDLVO analysis combined with dynamic light scattering (DLS), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analytical methods demonstrates that aggregation of MNPs is governed by the coupled action of electrostatic repulsion, steric repulsion, cation bridging, and patch-charge attraction, with the dominant interaction shifting in response to environmental conditions. A mechanistic understanding of the co-regulation by organic coatings and environmental factors provides a theoretical basis for designing highly stable and environmentally benign MNP-based remediation materials.

     

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