Research progress on coating application and mechanism based on MOF materials
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摘要: 金属有机骨架(MOF)作为一种新型多孔晶体材料，因其具有高孔隙率、结构多样、化学结构可控等特点可被作为纳米粒子和载体使用。基于MOF材料的涂层可兼具MOF本身的优点，但基于MOF材料的涂层应用和机制研究的综述性论文不多。本文针对基于MOF材料的涂层国内外研究现状进行了介绍，重点阐述了基于MOF材料的涂层防/除冰应用(超疏水表面和光滑液体注入多孔表面(SLIPS))、防腐应用(MOF材料作为纳米粒子和载体)和抗菌应用(基于金属离子释放、基于光动力(PDT)和基于光热(PTT))，并归纳出不同涂层的防/除冰机制(降低水的凝固温度和减少冰的黏附)、防腐机制(直接物理阻隔或生成化合物而达到阻隔效果)和抗菌机制(对真核细胞具有弱毒性的金属离子达到抗菌效果、活性氧(ROS)在光照射下激活达到抑菌效果和通过吸收外界光产生热量，随温度升高而达到抗菌效果)。并对基于MOF材料的涂层面临的关键挑战、潜在应用和发展前景进行了展望。Abstract: Metal-organic framework (MOF), as a new type of porous crystal material, can be used as nanoparticle and carrier because of its high porosity, diverse structure and controllable chemical structure. Functional coatings prepared based on MOF materials can combine the advantages of MOF and have a wide range of applications, but there are not many papers on the application and mechanism of coatings based on MOF materials. The research status of MOF-based coatings at home and abroad was introduced, focusing on the anti-icing/de-icing applications of MOF-based coatings (superhydrophobic surfaces and smooth liquid-injected porous surfaces (SLIPS)), anti-corrosion applications (MOF materials as nanoparticles and carriers) and antibacterial applications (based on metal ion release, photodynamic therapy (PDT) and photothermal therapy (PTT)), and the anti-icing mechanisms of different coatings (reducing the solidification temperature of water and reducing ice adhesion) were summarized. Antiseptic mechanism (direct physical barrier or formation of compounds to achieve the barrier effect) and antibacterial mechanism (metal ions with weak toxicity to eukaryotic cells achieve antibacterial effect, reactive oxygen species (ROS) are activated under light irradiation to achieve antibacterial effect, and heat is generated by absorbing external light, and antibacterial effect is achieved with increasing temperature). The key challenges, potential applications and development prospects of MOF-based coatings are prospected.
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图 1 (a)超疏水复合涂层制备过程；(b)不同基体的阻抗模量|Z|与频率关系的Bode图[19]
POTS—1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilanes; EP—Epoxy epoxide; PA—Polyamide; ZIF—Zeolitic imidazolate framework
Figure 1. (a) Superhydrophobic composite coating preparation process; (b) Bode plots of different matrix's relationship between impedance modulus |Z| and frequency[19]
图 6 裸Al板、原位水热生长制备的ZnAl-NO3层状双氢氧化合物(LDH)缓冲层、纯ZIF-8涂层和ZIF-8-ZnAl-NO3 LDH复合涂层的DC极化曲线[48]
E—Electrode potential; I—Current density
Figure 6. DC polarization curves for bare Al plates, ZnAl-NO3 layered double hydroxides (LDH) buffer layers prepared by in situ hydrothermal growth , pure ZIF-8 coatings and ZIF-8-ZnAl-NO3 LDH composite coatings[48]
图 9 (a)不同涂层在3.5wt%NaCl溶液中的|Z|0.01 Hz的值；不同涂层的防腐机制：(b) EP涂层；(c)普通填料涂层；(d) ZIF-8涂层[54]
Z0, Z1, Z3, Z5—Mass fraction of ZIF-8 in epoxy resin is 0wt%, 1wt%, 3wt%, 5wt%
Figure 9. (a) |Z|0.01 Hz value of different coatings in 3.5wt%NaCl solution; Anti-corrosion mechanism of different coatings: (b) EP coating; (c) Ordinary filler coating; (d) ZIF-8 coating[54]
图 17 (a)不同浓度AgNO3、PCN-224-透明质酸(HA)和PCN-224-Ag-HA在光照射下MRSA菌株的存活率；(b) PCN-224-Ag-HA纳米剂的制备及其抗菌机制示意图[81]
L—Light; PCN—Porous coordination network
Figure 17. (a) Survival rates of MRSA strain at different concentrations of AgNO3, PCN-224-hyaluronic acid (HA) and PCN-224-Ag-HA under light irradiation; (b) Preparation of PCN-224-Ag-HA nanoagen and schematic diagram of antibacterial mechanism[81]
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