MOFs/biomass matrix composites and their application progress
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摘要:
目的 MOFs具有比表面积大、孔隙度和孔径可调、表面修饰功能强、化学热稳定性好等优点被广泛应用于材料领域，然而，传统的MOFs材料存在成本高、分散性差、不可再生、固有刚性等缺点。生物质材料表面含有大量羟基及其他官能团，有助于MOFs中的活性基团及其它物质通过原位生长、层层组装等方法进行锚定，因此将MOFs与多种功能材料相结合，可结合两种材料的优点，实现价值最大化。本文从不同生物质原料出发概述了MOFs/生物质基复合材料的种类、制备方法，详细综述了该材料在多个领域应用的研究进展，并针对制备和应用过程中存在的问题提出了建设性的意见，以及为研究者设计和开发高性能MOFs/生物质复合材料提供科学的依据。 方法 本文从生物质的原料出发，概述了MOFs/生物质基复合材料的种类、制备方法，详细综述了该材料在水体净化、气体分离、抗菌处理、电化学应用方面的研究进展，并分析复合材料再应用过程中的作用机制，总结了MOFs/生物质复合材料在性能提升方面面临的问题。 结果 通过总结MOFs/生物质复合材料制备、性能以及应用三方面的文献发现，MOFs与生物质的结合为制备高性能功能材料提供了新的思路。在MOFs/生物质材料中，生物质为MOFs提供了机械支撑，并赋予了更高的孔隙率和更大的比表面积。生物质不仅解决了MOFs的聚集问题，还连接了独立的MOFs晶体，显著提高了MOFs的性能。因此，与传统MOFs相比，以生物质材料为配体的MOFs/生物质复合材料在吸附、抗菌处理、电化学领域具有更强的吸引力。 结论 现今，有关MOFs材料的设计、合成和应用方面的研究逐年大幅增加，但是由于MOFs材料的特殊性，MOFs/生物质复合材料的研究还存在很大的发展空间。具体如下:(1)研发低成本MOFs/生物质复合材料。虽然生物质来源于丰富的自然资源，但其收集、运输、加工和处理过程成本较高；部分MOFs依然存在合成过程复杂、零售价格高等问题，这极大地阻碍了其大规模应用。因此，进一步寻找更合适的生物质资源以及研发更环保低成本的技术来实现MOFs/生物质材料的产业化至关重要。(2) 开发更简便的复合材料合成方法。建议考虑将热容积法与原位生长法相结合来制备MOFs/生物质复合材料，深入研究MOFs与生物质的复合机制，通过优化反应参数(如时间、温度、浓度和pH)，备出具有良好的结晶度、高比表面积、有序结构以及较大负载率的复合材料。 (3)优化复合材料基底和MOFs的结构。基底的结构为导电、离子通过、基团结合或其他可与MOFs应用相关的特性提供内在通道。通过调整生物质材料之间的3D结构和连接方式，提供更多的反应位点，从而实现高效和畅通的离子或电流传输等性能。 (4) 进一步拓展MOFs/生物质复合材料在电磁屏蔽、光学、食品、智能穿戴等新兴领域的应用。另外，优化MOFs的结构，更有利于相应复合材料性能稳定性的提升和应用的拓展。 Abstract: Abstracts : Metal-organic frameworks (MOFs) are widely used in materials because of their large specific surface area, adjustable porosity and pore size, strong surface modification function, and good chemical and thermal stability. However, MOFs are prone to agglomeration, and their inherent crystal structure leads to poor flexibility, processability and recyclability, which severely limits their application. In recent years, MOFs have been compounded with environmentally friendly and renewable biomass materials, which not only solves the above problems, but also combines the advantages of biomass and MOFs to realize their application in emerging fields. Starting from different biomass raw materials, this paper introduces the types and preparation methods of MOFs/biomass matrix composites, reviews the research progress of MOFs/biomass matrix composites in water purification, gas separation, antibacterial treatment and electrochemical application in detail, and puts forward constructive suggestions for the problems existing in the preparation and application process, in order to provide a scientific basis for researchers to design and develop high-performance MOFs/biomass composites.-
Key words:
- metal-organic frameworks (MOFs) /
- biomass /
- composites /
- antibiosis /
- adsorption /
- air purification /
- electrochemistry
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图 1 复合材料相关示意图
MOFs/生物质复合材料: (a)ZIF-8/木材复合材料的制备过程 [15]；(b)ZIF-8沉积在管腔表面示意图[15]； (c) UiO-66/玉米秸秆的合成和一体式装置的设计示意图[18]；(d) MS细胞壁的表面的SEM图像 [18]；MOFs/生物质提取物复合材料：(e)Co/C/CNF气凝胶制备示意图[28]
Figure 1. Schematic diagram of composite materials
MOFs/wood composites: (a)Schematic diagram of the preparation process of ZIF-8/wood composite; (b)Schematic diagram of ZIF-8 deposition on the surface of the lumen; (c)Schematic diagram of the design of the synthesis and integrated unit of UiO-66/corn stover; (d)SEM image of the surface of the MS cell wall; MOFs/ Biomass extract composites: (e)Schematic diagram of Co/C/CNF aerogel preparation
图 2 MOFs吸附去除有害物质的可能机制示意图[30]
Figure 2. Schematic diagram of the possible mechanism of MOFs adsorption to remove harmful substances
图 3 MOF/生物质基材料水体净化应用相关示意图
有机化合物的去除：(a)在三维木膜中生长 UiO-66 粒子制备的 UiO-66/Wood 过滤膜材料示意图[33]；(b)三层过滤器在不同流速下对每种有机污染物的去除效率[33]；(c)三层过滤器连续再生循环的吸附效率[33]；(d)制备WC-Co炭化材料示意图[34]；(e)不同材料对CR、 MB的吸附能力[34]；金属离子的去除：(f)制备BC/ZIF-8示意图[35]；(g) BC/ZIF-8对Pb2+的吸附能力[35]；(h) BC，ZIF-8和BC@ZIF-8纳米颗粒对Pb2+的吸附效率对比[35]；(i)制备的ZIF-67/BC/壳聚糖气凝胶去除重金属离子和有机污染物示意图[23]；(j) BC、BC/壳聚糖和ZIF-67/BC/壳聚糖气凝胶对Cu2+和Cr6+的吸附能力对比[23]；(k) ZIF-67/BC/壳聚糖气凝胶连续循环对Cr2+、Cu2+的吸附效率[23]
Figure 3. Schematic diagram of MOF/biomass-based material water purification application
Removal of organic compounds: (a) Schematic diagram of UiO-66/Wood filter membrane material prepared by growing UiO-66 particles in a three-dimensional wood membrane; (b) The removal efficiency of the three-layer filter for each organic contaminant at different flow rates; (c) Adsorption efficiency of continuous regeneration cycle of three-layer filter; (d) Schematic diagram of WC-Co carbonized material preparation; (e) Adsorption capacity of different materials for CR and MB; Removal of metal ions: (f) Schematic diagram of BC/ZIF-8 was prepared; (g) Adsorption capacity of BC/ZIF-8 to Pb2+; (h) Comparison of adsorption efficiency of BC， ZIF-8 and BC@ZIF-8 nanoparticles on Pb2+; (i) Schematic diagram of ZIF-67/BC/chitosan aerogel for removal of heavy metal ions and organic pollutants; (j) Comparison of adsorption capacity of BC, BC/chitosan and ZIF-67/BC/chitosan aerogels on Cu2+ and Cr6+; (k)Adsorption efficiency of ZIF-67/BC/chitosan aerogel by continuous cycling of Cr2+ and Cu2+
图 4 MOF/生物质基材料空气净化应用相关示意图
(a) ZIF-8/CNF复合膜中CO2传输的示意图[37]；(b) Ag-MOFs/CNF/ZIF-8过滤器的结构和过滤机制[39]；(c) 不同过滤器的过滤能力[39]。
Figure 4. Schematic diagram of MOF/biomass-based material air purification application
(a) Schematic diagram of CO2 transport in ZIF-8/CNF composite film; (b) Structure and filtration mechanism of Ag-MOFs/CNF/ZIF-8 filters; (c) Filtering capabilities of different filters
图 5 MOF/生物质基材料生物医学应用相关示意图
(a) MOFs抗菌机制示意图[22]; (b)不同过滤器对大肠杆菌的抗菌性能[34]; (c) PDA/ZIF-8/CNFs在近红外光或低pH辐射下的药物释放[48]; (d) NIR光照和pH值对PDA@ZIF-8/CNFs复合水凝胶药物释放的影响[48]
Figure 5. Schematic diagram of the biomedical application of MOF/biomass-based materials
(a) Schematic diagram of the antibacterial mechanism of MOFs; (b) Antimicrobial properties of different filters against E. coli; (c) Drug release of PDA/ZIF-8/CNFs in near-infrared light or low pH radiation; (d) Effects of NIR light and pH on drug release of PDA@ZIF-8/CNFs complex hydrogels
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