高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (8): 1776-1784.doi: 10.7503/cjcu20200183

• 分析化学 • 上一篇    下一篇

基于金属卟啉2DMOFs仿酶催化的过氧化氢比色法检测

谢兴钰, 赵雅香, 赵莉芝, 李日舜, 吴迪昊, 叶卉, 辛清萍, 李泓, 张玉忠   

  1. 天津工业大学省部共建分离膜与膜过程国家重点实验室, 材料科学与工程学院, 天津 300387
  • 收稿日期:2020-04-07 出版日期:2020-08-10 发布日期:2020-07-31
  • 通讯作者: 赵莉芝,女,博士,副教授,主要从事仿酶催化与膜分离方面的研究.E-mail:zhaolizhi_phd@163.com E-mail:zhaolizhi_phd@163.com
  • 基金资助:
    国家重点研发计划(批准号:2017YFC0404001)、国家自然科学基金(批准号:21978216)和天津市大学生创新创业训练计划项目(项目号:201810058083)资助.

Colorimetric Detection Method for H2O2 Based on Two-dimensional Metal-organic Frameworks of Metalloporphyrin

XIE Xingyu, ZHAO Yaxiang, ZHAO Lizhi, LI Rishun, WU Dihao, YE Hui, XIN Qingping, LI Hong, ZHANG Yuzhong   

  1. State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China
  • Received:2020-04-07 Online:2020-08-10 Published:2020-07-31
  • Supported by:
    Supported by the National Key Research and Development Project, China(No.2017YFC0404001), the National Natural Science Foundation of China(No.21978216) and the Tianjin Undergraduate Training Program for Innovation and Entrepreneurship, China(No. 201810058083).

摘要: 以四(4-羧苯基)铁卟啉(FeTCPP)作为有机配体,铜离子作为金属节点,利用溶剂热法制备了双金属Cu-FeTCPP金属有机骨架(MOFs)材料,并采用表面活性剂辅助法合成了二维纳米片(Cu-FeTCPP 2DMOFs).该纳米片呈超薄的纳米结构,与三维块体结构(3DMOFs)相比具有更大的比表面积.基于Cu-FeTCPP 2DMOFs的仿酶特性,将其用于催化过氧化氢(H2O2)氧化底物3,3',5,5'-四甲基联苯胺(TMB)显色,根据显色产物吸光度与H2O2浓度之间的正比关系实现了对H2O2的测定.经稳态动力学分析发现,底物相同时该纳米片的米氏常数Km均比Cu-FeTCPP 3DMOFs的Km小,表明纳米片与底物之间有更好的亲和力,这归因于二维结构大的比表面积和较多易接近的活性位点.基于Cu-FeTCPP 2DMOFs构建的比色检测方法在优化条件下对H2O2的线性检测范围为3~1000 μmol/L,检出限为2.08 μmol/L,在水体中H2O2的检测方面具有良好的应用前景.

关键词: 金属卟啉, 金属有机骨架, 仿酶, H2O2检测

Abstract: Using iron tetra(4-carboxyphenyl)porphyrin(FeTCPP) as the organic ligand and copper ions as the metal nodes, the metal-organic frameworks(MOFs) of bimetallic Cu-FeTCPP were prepared by solvothermal method, and the two-dimensional ultrathin nanosheets(Cu-FeTCPP 2DMOFs) were synthesized by a surfactant-assisted method. Compared with the three-dimensional bulk MOFs(3DMOFs), the nanosheets had ultra-thin nanostructures and larger specific surface area. Cu-FeTCPP 2DMOFs with enzyme-like properties can catalyze the chromogenic oxidation of the substrate 3,3',5,5'-tetramethylbenzidine(TMB) by hydrogen peroxide(H2O2). The proportional relationship between the absorbance of the reaction products and the concentration of H2O2 enabled the determination of H2O2. In the steady state kinetic analysis, the Michaelis constants Km of the nanosheets were smaller than those of Cu-FeTCPP 3DMOFs, indicating that the nanosheets showed better affinity to the substrates. This is attributed to the larger specific surface area of ​​the 2D ultrathin structure and the higher accessibility of active sites. The colorimetric detection method for H2O2 based on Cu-FeTCPP 2DMOFs had a linear detection range of 3-1000 μmol/L and a limit of detection(LOD) of 2.08 μmol/L, showing application prospects in the detection of H2O2 in water.

Key words: Metalloporphyrin, Metal-organic framework, Enzyme mimics, H2O2 detection

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