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血红素-葡萄糖氧化酶级联催化体系的构建和应用
Development and Application of Hemin-Glucose Oxidase Cascade Catalytic System
【摘要】 天然生物酶具有催化活性高、特异性强的优点,而其对环境非常敏感;纳米酶等酶模拟物具有更高的稳定性,可以作为生物酶的有效替代和补充参与催化反应。酶催化和类芬顿反应的结合在环境污染物降解领域显示出巨大的潜力,金属有机框架(MOFs)材料可以做为生物酶和其他功能分子的载体。采用原位沉淀法制备了氯高铁血红素(Hemin)和葡萄糖氧化酶(GOx)包埋在ZIF-8 MOFs骨架中的复合材料(Hemin@GOx@ZIF-8),其在水溶液中具有良好的分散性,溶液呈墨绿色。结构表征Hemin和GOx能够被成功地封装在ZIF-8骨架中,并且复合材料仍能完整保持ZIF-8的骨架结构。复合材料Hemin@GOx@ZIF-8为多孔晶体结构,粒径约为300 nm;比表面积为1 512 m2·g-1;平均孔径1.076 nm;孔体积约为0.607 5 cm3·g-1。丰富的比表面积和孔容量,可以为催化反应提供更多活性位点,从而有利于提高催化反应效率。复合材料Hemin@GOx@ZIF-8具有良好的稳定性。该复合材料具有级联催化的性能,在葡萄糖驱动下,GOx可将葡萄糖催化氧化生成H2O2,并被复合材料中的Hemin催化发生类芬顿反应,从而实现对有机污染物高效的级联催化降解。以有机染料刚果红(CR)为底物研究该级联体系的催化降解性能,其对水溶液中CR的降解率达到88%以上,该级联催化体系还具有良好的热稳定性、有机溶剂耐受性和重复利用性。进一步研究表明,Hemin@GOx@ZIF-8级联降解体系对不同类型有机污染物均具有良好的降解能力,在环境污染物降解领域具有良好的应用前景。
【Abstract】 Natural biological enzymes have the advantages of high catalytic activity and selectivity, while they are usually sensitive to the matrix and extreme environmental conditions. Nano-enzymes with higher stability can be effective substitutes and supplements for biological enzymes in catalytic reactions. Enzyme catalysis and Fenton-like reactions have shown great potential in environmental pollutant degradation. Metal-organic frameworks(MOFs) are excellent carriers for biological enzymes and other functional molecules. The in-situ precipitation method prepared ZIF-8 composites of hemin and glucose oxidase(Hemin@GOx@ZIF-8). Hemin@GOx@ZIF-8 has good dispersibility in an aqueous solution, and the solution appears dark green. The structure characterization showed that Hemin and GOx could be successfully encapsulated in the ZIF-8 framework, and the skeleton structure of ZIF-8 remained intact. Hemin@GOx@ZIF-8 has a porous structure with an average particle size of 300 nm, a specific surface area of 1 512 m2·g-1, an average aperture of 1.076 nm, and a pore volume of about 0.607 5 cm3·g-1. Large specific surface area and pore volume can provide more active sites for catalytic reactions, which improves catalytic efficiency. Hemin@GOx@ZIF-8 has good stability and cascade catalytic performance. Under glucose drive, H2O2 is generated from reactions catalyzed by GOx, then catalyzed by Hemin to complete the Fenton-like reaction. Thus, organic pollutants are efficiently catalyzed and degraded in this cascade catalytic system. The catalytic degradation performance of the cascade system was studied using the organic dye Congo Red(CR) as the substrate. The results indicated that the degradation rate of CR in aqueous solution reached over 88%. The cascade catalytic system has good thermal stability, organic solvent resistance, and repeatability. Further research indicated that Hemin@GOx @ZIF-8 has good degradation ability for some different organic pollutants in water. So this cascade catalytic system has important practical significance and good application prospects in environmental pollutant degradation.
【Key words】 Cascade catalysis; Glucose oxidase; Hemin; Fenton-like reaction; Pollutant degradation;
- 【文献出处】 光谱学与光谱分析 ,Spectroscopy and Spectral Analysis , 编辑部邮箱 ,2025年02期
- 【分类号】X703
- 【下载频次】49