Synthesis Of Nanometer Peroxide Mimic Enzyme Based On Copper-based Metal Organic Framework And Its Sensing Application

This paper first briefly introduces the synthesis of metal organic framework materials and their application as peroxide mimic enzymes.Based on this,the design,preparation,morphology and size control of copper-based metal organic framework materials（Cu-MOF）and their applications in H₂O₂ reduction are studied.In this paper,there are two main aspects of work have been carried out:（1）Polyvinylpyrrolidone-assisted synthesis of Cu-MOF nanoparticles and its application in peroxide mimic enzymesPolyvinylpyrrolidone（PVP）can be used as a surface stabilizer or a growth regulator to control the sizes and morphologies of materials,and the role of PVP in synthesis depends on the type of complex and reaction conditions.Based on this,this paper designed a method of morphology and size control of Cu-MOF with PVP,and successfully regulated the morphology and size of Cu-MOF.The morphologies of materials have been changed from irregular micron-sized blocks to uniform and regular nano-sized spheres（Cu-MOF Ns）with the help of PVP.To characterize the materials.We used FTIR,XRD and XPS.The experiments showed that the introduction of PVP had an effect on the valence of the active neutral Cu.The catalytic active center of Cu-MOF Ns was Cu^Ⅱ/Ⅰ-（COO）.And came up with a reasonable mechanism of PVP regulation based on this.Later,the regulated Cu-MOF Ns were applied to hydrogen peroxide catalysis,and it was found that Cu-MOF Ns,as a new type of peroxide mimic enzyme,can effectively reduce hydrogen peroxide,and can be a new kind of H₂O₂ biosensor.The catalytic capacity of Cu-MOF Ns is better than unregulated Cu-MOF,which can be attributed to the larger specific surface area and the exposure of more active sites.The detection limit of H₂O₂is 0.331μM,the sensitivity is 0.005μA/μM,and the linear range is 10-5692μM.（2）2-methylimidazole-assisted synthesis of double-ligand amino-functionalized Cu-MOF nanoparticles and its application in peroxide mimic enzymesAs two common ligands of MOF,2-MI and-COOH can be coordinated with a kind of metal ions at the same time.Based on this,this paper have been successfully synthesized a new double-ligand amino-functionalized Cu-MOF（Cu-MI-MOF Ns）with two coordination structures of Cu-N-C and Cu-OOC with the introduce of 2-methylimidazole.It was found that the addition of 2-MI will change the morphology and size of Cu-MI-MOF Ns,which is attributed to 2-MI as a competing ligand,can inhibit the nucleation rate to control the size of the material with analysis of structure.And it was found that the introduction of 2-MI can accelerate the deprotonation of 2-aminoterephthalic acid in the solution,so that Cu-MOF can be prepared at normal temperature and pressure.Subsequently,Cu-MI-MOF Ns was applied to hydrogen peroxide catalysis.It was found that Cu-MI-MOF Ns,as a new type of peroxide mimic enzyme,can effectively reduce hydrogen peroxide and can be H₂O₂ biosensor.The detection limit of H₂O₂ is 3.2μM,the sensitivity is 0.00156μA/μM,and the linear range is 10-13290μM.