2.华南理工大学华南协同创新研究院,东莞 523808
1.College of Environment and Energy, South China University of Technology, Guangzhou 510006, China
2.South China Institute of Collaborative Innovation, South China University of Technology, Dongguan 523808, China
通过溶剂热合成法制备了水稳定性的铁基金属有机骨架材料MIL-88B(Fe),并将辣根过氧化酶(HRP)以共价固定法负载在MIL-88B(Fe)上得到MIL-88B(Fe)/HRP复合材料,并用于降解双酚A (BPA)。通过XRD、FTIR、SEM和TGA等手段对材料进行了表征。结果表明,HRP成功固定在MIL-88B(Fe)表面,没有改变MIL-88B(Fe)的形貌和晶体结构;在添加亲水剂聚乙二醇后,MIL-88B(Fe)/HRP可高效去除BPA,1 h内BPA去除率可达99.2%。分别考察了PEG用量、BPA初始质量浓度、固定化酶投加量等对降解效率的影响。结果表明,在PEG/BPA质量比0.4、pH = 7、25 ℃、BPA初始质量浓度20 mg·L
的条件下,3 h内可去除98.4%的BPA。此外,MIL-88B(Fe)/HRP复合材料具有较好的稳定性和可重复使用性,固定化HRP的贮存稳定性、热稳定性均优于游离HRP,循环使用4次后,固定化HRP的残余活性仍高于80%。以上研究结果可为新型酶固定材料的开发及其在废水处理中的应用提供参考。
In this study, a water-stable Fe-based metal-organic framework material of MIL-88B (Fe) was prepared through a solvothermal method, then horseradish peroxidase was immobilized on MIL-88B (Fe) using covalent fixation method to prepare MIL-88B (Fe)/HRP composite for the degradation of bisphenol A (BPA). The material was characterized via XRD, FTIR, SEM and TGA methods. The results showed that HRP was successfully immobilized on MIL-88B(Fe) without changing its morphology and crystal structure. The BPA degradation experiments showed that MIL-88B(Fe)/HRP could effectively remove BPA by adding the hydrophilic agent polyethylene glycol, and the removal rate of BPA was up to 99.2% within 1 h. The effects of PEG dosage, initial BPA concentration and immobilized enzyme dosage on the BPA degradation efficiency were investigated. The results showed that at PEG/BPA mass ratio of 0.4, pH=7, 25 ℃, initial BPA concentration of 20 mg·L
, 98.4% BPA could be removed within 3 h. At the same time, MIL-88B(Fe)/HRP had good stability and reusability. The storage stability and thermal stability of immobilized HRP were better than that of free HRP. After 4 cycles, the residual activity of immobilized HRP was still more than 80%. This study provides a reference for the development of new enzyme fixation materials and their application in wastewater treatment.
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MIL-88(Fe)和MIL-88(Fe)/HRP的SEM图谱
SEM images of (a) MIL-88(Fe), (b) MIL-88(Fe)/HRP
MIL-88(Fe)和MIL-88(Fe)/HRP的XRD图谱
XRD patterns of MIL-88B(Fe) and MIL-88B(Fe)/HRP
HRP、MIL-88(Fe)和MIL-88(Fe)/HRP的FTIR图谱
FTIR spectra of HRP, MIL-88B(Fe) and MIL-88B(Fe)/HRP
MIL-88(Fe)和MIL-88(Fe)/HRP的TGA图谱
TGA curves of MIL-88B(Fe) and MIL-88B(Fe)/HRP
Removal rate of BPA by catalytic materials under different conditions
Effect of PEG dosage on the removal rate of BPA
Effects of different degradation conditions on the degradation of BPA
游离和固定化HRP的米氏方程图和Lineweaver-Burk图
Michaelis-Menten plots and Lineweaver-Burk plots of free and immobilized HRP
Stability of free and immobilized HRP
Reusability of immobilized HRP
MIL-88 (Fe)/HRP降解BPA前后的XRD图谱
XRD patterns before and after BPA degradation by MIL-88B(Fe)/HRP
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