Synthesis And Electrochemical Sensing Applications Of Binary Or Ternary Metal MOFs Derivatives

With the development of science,some pollutants harmful to the human body have entered the human body through various channels.Most of the higher-level pollutants can be detected by conventional detection methods.But some of the pollutants which are low in content and harmful to the human body can not achieve sensitive detection by conventional detection methods.In addition,accurate analysis of changes in the content of disease markers is helpful for early diagnosis of diseases.However,the content of markers in most diseases is low,which still poses a challenge for sensitive detection.Due to its high sensitivity,simplicity and rapidity,electrochemical sensors have been widely used in the detection of environmental pollutants and disease markers.As electrode modification,the binary and ternary metal organic framework compound?MOF?derived materials have great potential due to their good electrical conductivity,abundant pore structure,large specific surface area and composite synergistic effect.Based on this,this paper has done the following research:1.Firstly,the research progress and classification of electrochemical sensors are reviewed.Then the research progress of MOFs and their derived binary or ternary metal oxides is introduced.Finally,the application of binary and ternary metal MOF derivatives in electrochemistry is introduced.2.Fe-Mn-MOF materials was synthesized with terephthalic acid as ligand and Fe²⁺and Mn²⁺as central metal ions,and the Fe₂O₃@MnO oxide composite was obtained by high temperature calcination Fe-Mn-MOF.Moreover,Fe₂O₃@MnO was characterized by SEM and EDS,and twokinds of electrochemical sensors were constructed.Firstly,the modified electrode which prepared by immobilizing myoglobin?Mb?with Fe₂O₃@MnO was used to construct a hydrogen peroxide electrochemical enzyme sensor which minimum detection concentration is 10?M.Nextly,a human immunoglobulin IgG immunosensor was constructed with Fe₂O₃@MnO as a modification material.The immunosensor whose linearity was in the range of 0.05-0.5and 0.5-50 ng/mL respectively and detection limit was 0.02 ng/mL has a good detection performance on immunoglobulin IgG.The detection performance of IgG immunosensor constructed by Fe₂O₃@MnO material is better than H₂O₂ sensor.3.The Ni-doped Co/CoO/NC material was obtained under nitrogen by calcination Binary metal MOF?Ni-Co-ZIF?which was synthesized by using 2-methylimidazole as ligand and Ni²⁺and Co²⁺ion as the central metal ion.The material was characterized by SEM.The NO₂^-sensor was constructed by immobilizing Mb with the material.The linear range of the sensor is 0.8-1050?M and 1050-2050?M,respectively,with a detection limit of 0.3?M.Then Ni-doped Co/CoO/NC was used to construct two organophosphorus pesticide sensors.For methyl parathion,the linear range was5.0×10^-12-5.0×10^-88 g·mL^-11 and the detection was 1.8×10^-1212 g·mL^-1;for paraoxon,the linear range was 1.0×10^-13-1.0×10^-10g·mL^-1g·mL^-1and the detection was 4.6×10^-14g·mL^-1.It is shown that the NO₂^-and two organophosphorus sensors constructed by Ni-doped Co/CoO/NC composite have lower detection limit and wider linear range.4.ZIF-8@FeOOH@ZIF-67 was synthesized by using FeOOH composite ZIF-67and ZIF-8.The ZnO-FeO-CoO material was obtained by calcinating ZIF-8@FeOOH@ZIF-67 at 800? in air.The morphological characterization and elemental content of ZnO-FeO-CoO were characterized by SEM and EDS.Subsequently,the electrocatalytic properties of 1-NAP and 2-NAP were studied by cyclic voltammetry?CV?and electrochemical impedance spectroscopy?EIS?and differential pulse voltammetry?DPV?,indicating that the ZnO-FeO-CoO material has a good electrocatalytic properties for two naphthols.A new electrochemical method for the determination of naphthol was established.For 1-NAP,the linear range was 0.4-20?M and the detection limit was 0.16?M;For 2-NAP,the linear range was 0.5-50?M and the detection limit was 0.18?M.The peak potentials of 1-NAP and 2-NAP are 0.384V and 0.568V respectively.Therefore,the simultaneous detection of 1-NAP and 2-NAP in samples can be realized.