The Synthesis And Applications Of Copper-tri(Carboxyphenyl) Benzene Organic Gel And Its Derivative

Metal-organic gel?MOG?is an emerging smart soft material that mainly is rapidly straightforwardly self-assembled from metal ions and organic ligands through metal-ligand interactions and intermolecular force such as hydrogen bonding,Van der Waals force,?-?stacking and so on.MOG has potential application prospects in the fields of adsorption,catalysis,sensing,and biomedicine due to their intrinsic and desirable characteristics of porosity,large surface area,low molecular weight and high thermal stability.The existing reports concerning the use of MOGs as absorbents described problems with low adsorption efficiency,long adsorption time or unrecyclability.Therefore,it is worth further exploring novel porous MOG materials for efficient adsorption of organic dyes.Moreover,there are relatively few studies on the preparation of transition metal oxides?TMOs?by MOG as a precursor.Copper oxide?CuO?,an important member of the TMOs family,is considered as a promising catalytic material owing to its abundant active sites,chemical stability,low-cost and environmental benignity.Accordingly,copper-tri?carboxyphenyl?benzene organic gel?Cu-MOG?was used as the research object,and its application in dye adsorption was discussed.Moreover,the preparation and analytical applications of CuO nanoparticles?CuO-NPs?derived from Cu-MOG were studied.The specific research contents are as follows:?1?The preparation and applications of copper-tri?carboxyphenyl?benzene organic gel in dyes adsorptionCu?II?-based metal-organic gel?Cu-MOG?with three-dimensional network fiber porous structure prepared by simply mixing 1,3,5-tri?4-carboxyphenyl?benzene?H₃BTB?with copper sulfide?CuSO₄·5H₂O?.The prepared Cu-MOG showed excellent adsorption performance for cationic dyes,with an adsorption capacity of up to 650.32 mg/g,adsorption efficiency?adsorption of 80%neutral red in 1 minute?and good recycling.The high adsorption efficiency was attributed to its large specific surface area and nanoporous structure.The principle is mainly that negatively charged Cu-MOG massively bind cationic dyes through electrostatic interaction,and the porous structure of Cu-MOG can promote intra-pore diffusion of dye molecules.Additionally,the Cu-MOG displayed size-selective adsorption,based on adsorption studies concerning dyes of different sizes as calculated by density functional theory?DFT?.?2?The preparation of CuO nanoparticles derived from copper-tri?carboxyphenyl?benzene organic gel and there application in biomolecules detectionCuO nanoparticles?CuO-NPs?with high surface area were prepared by directly pyrolyzing copper-tris?carboxyphenyl?benzene organic gel?Cu-MOG?precursor.And the prepared CuO-NPs were successfully used to build a multifunctional analytical sensing platform.The obtained CuO-NPs could decompose H₂O₂ to produce hydroxyl radical?·OH?;?·OH?catalyzed the oxidation of 3,3',5,5'-tetramethylbenzidine?TMB?to blue TMB oxide.CuO-NPs can be further used as mimic enzymes for sensitively and rapidly detecting cholesterol by utilizing the principle that cholesterol generates H₂O₂under the action of cholesterol oxidase.A good linearity of cholesterol was performed in the range from 1?M to 15?M with the detection limit of 0.43?M.Moreover,CuO-NPs also showed excellent electrocatalytic activity for glucose oxidation due to its characteristics of high specific surface area,multiporosity and a large number of exposed metal active sites.So it can be used for for electrochemical detecting glucose.The wide linear range of glucose was from 5 to 600 mM;the detection limit and sensitivity were 0.59?M and 1098.37 A/?mM·cm²?,respectively.Additionally,CuO-NPs also exhibited excellent photoelectrochemical?PEC?performance based on the narrow band gap?1.20 V?and the presence of intrinsic defects.Cu-S bond formed by the combination of L-Cys and CuO-NPs would greatly reduce the photocurrent signal of CuO-NPs.Therefore,CuO-NPs could be used as a PEC sensor to detect L-Cys,which exhibited wide linear range from 0.1?M to 6?M and low detection limit of 0.04?M.In conclusion,this thesis focused on the research of Cu-MOG.First,the application of Cu-MOG in dye adsorption was investigated.Next,CuO-NPs were synthesized by calcining Cu-MOG precursor.The enzyme-mimicking catalytic activity,electrocatalytic properties and photoelectrochemical?PEC?properties of CuO-NPs were used to analyze and detect cholesterol,glucose,and L-Cys,respectively.These studies not only open the window for exploring MOG as an effective adsorbent,but also broaden the application of MOG as a precursor to synthesize multifunctional nanostructured transition metal oxides?TMOs?.