MOFs/biomass matrix composites and their application progress
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摘要: 金属有机框架(MOFs)因其具有比表面积大、孔隙度和孔径可调、表面修饰功能强、化学和热稳定性好等优点而被广泛应用于材料领域。然而，MOFs容易团聚，其固有的晶体结构导致其柔韧性、加工性和可回收性较差，严重限制了其应用。近年来，MOFs与环保可再生的生物质材料复合，不仅解决了上述问题，且兼有生物质和MOFs两种材料的优势，实现了其在新兴领域的应用。从不同生物质原料出发，介绍了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，并针对制备和应用过程中存在的问题提出了建设性的意见，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。Abstract: 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.
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Key words:
- metal-organic frameworks (MOFs) /
- biomass /
- composites /
- antibiosis /
- adsorption /
- air purification /
- electrochemistry
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图 1 金属有机框架(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[17]；(d) MS细胞壁表面的SEM图像[17]；MOFs/生物质提取物复合材料：(e) Co/C/CNF气凝胶制备示意图[22]
ZIF—Zeolitic Imidazolate Frameworks; H2BDC—2-hydroxyterephthalic acid; MS—Corn stalks; UiO—Universitetet i Oslo; CNF—Cellulose nanofibers
Figure 1. Metal-organic frameworks (MOFs)/wood composites: (a) Schematic diagram of the preparation process of ZIF-8/wood composite[15]; (b) Schematic diagram of ZIF-8 deposition on the surface of the lumen[15]; (c) Schematic diagram of the design of the synthesis and integrated unit of UiO-66/corn stover[17]; (d) SEM image of the surface of the MS cell wall[17]; MOFs/biomass extract composites: (e) Schematic diagram of Co/C/CNF aerogel preparation[22]
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UiO-66/wood过滤膜材料的示意图[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) 制备碳化木(WC)-Co炭化材料示意图[34]；(e) 不同材料对刚果红(CR)、亚甲基蓝(MB)的吸附能力[34]；金属离子的去除：(f) 制备细菌纤维素/2-甲基咪唑锌(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]
TPA—Terephthalic acid; BPS—Brominated polystyrene; 1-NA—Azo dye precursors; BPA—Bisphenol-A; NPC—Nanoporous carbon; Qt—Adsorption capacity at time t
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) 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 wood composites (WC)-Co carbonized material preparation; (e) Adsorption capacity of different materials for congo red (CR) and methylene blue (MB); Removal of metal ions: (f) Schematic diagram of bacterial cellulose/zeolitic imidazolate framework-8 (BC/ZIF-8) 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；(b) Ag-MOFs/CNF/ZIF-8过滤器的结构和过滤机制[38]；(c) 不同过滤器的过滤能力[38]
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[38]; (c) Filtering capabilities of different filters[38]
图 5 MOFs/生物质基材料生物医学应用相关示意图：(a) MOFs抗菌机制[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[47]；(d) NIR光照和pH值对PDA@ZIF-8/CNFs复合水凝胶药物释放的影响[47]
PDA—Polydopamine; NIR—Near infrared
Figure 5. Schematic diagram of the biomedical application of MOFs/biomass-based materials: (a) Schematic diagram of the antibacterial mechanism of MOFs[22]; (b) Antimicrobial properties of different filters against E. coli[34]; (c) Drug release of PDA/ZIF-8/CNFs in near-infrared light or low pH radiation[47]; (d) Effects of NIR light and pH on drug release of PDA@ZIF-8/CNFs complex hydrogels[47]
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