Study On Preparation And Green Catalytic Properties Based On Cu/MIL-101

Objective:To promote the concept of“green chemistry”and sustainable development,this thesis aims to prepare Cu/MIL-101 heterogeneous catalysts by new methods and developed some heterogeneous catalytic reactions that were environmentally friendly and highly atomic.1.Synthesis and characterization of MIL-101MIL-101 was synthesized by hydrothermal method that using chromium nitrate and terephthalic acid as raw materials.The structure of MIL-101 was characterized by PXRD,SEM,N₂ adsorption-desorption experiments.Methods:1.Synthesis and characterization of MIL-101MIL-101 was synthesized by hydrothermal method that using chromium nitrate and terephthalic acid as raw materials.The structure of MIL-101 was characterized by PXRD,SEM,N₂ adsorption-desorption experiments.2.Synthesis and characterization of Cu/MIL-101The Cu/MIL-101 was prepared that NaBH₄ as reducing agent and the pectin as protective agent using CuCl₂ as the Cu precursor.The structure of Cu/MIL-101 and the distribution,valence state,content of copper nanoparticles were characterized by HRTEM,PXRD,EDS,XPS and ICP.3.Cu/MIL-101 heterogeneously catalyzed organic reactionTo synthesis 1,2,3-triazoles,1,3-butadiynes,?-ketophosphonates,pyridazines and propargylamines by Cu/MIL-101 as catalyst,the structure of products were Characterized by ¹H NMR,¹³C NMR.Results:The Cu/MIL-101 catalyst with uniform dispersion,good shape and stable properties was prepared.The particle size of the copper nanoparticles was about 5 nm and the mass percentage was 1.34%.The catalyst could efficiently catalyze the following reactions:1.In the aqueous phase,Cu/MIL-101 could catalyze the three-component Click reaction with benzyl bromide,substituted alkyne,sodium azide as substrate,and Cu/MIL-101 showed excellent catalytic activity for various 1,4-disubstituted-1,2,3-triazole.In addition to the substituted benzyl bromide,the precursor of the azide also included epoxide,2-bromoacetophenone and arylboronic acid,which were capable of obtaining the target compound in high yield at room temperature.2.To catalyze the synthesis of 1,3-butadiyne compounds by using substituted alkynes as substrates,the reaction had a wide range of substrates,including alkynes,heterocyclic alkynes and acetylenic alcohols,the alkynes had containing electron-withdrawing substituents and electron-donating substituents.A series of symmetric and asymmetric 1,3-butadiene structural units were produced in a medium or higher yield.When the substituent contained on the alkyne with a stronger electron withdrawing property,the reaction was hard,the yield was lower,or even the less.3.Without the presence of oxygen,to catalyze the synthesis of?-ketophosphonate compounds that the H-phosphonates and substituted alkynes as substrates.The reaction had the advantages of large substrate range and high yields,this reaction had certain potential in catalyzing the oxidation of phosphinic acid.4.To catalyze multi-component C-C coupling reaction with 2-pyridinecarb-oxaldehyde,secondary amine and substituted alkyne as a substrate in one pot to form pyridazine derivatives.The reaction had the advantages of large substrate range,and the target product can be obtained in a medium or higher yield.The method was synthesis an pyridazine derivatives structure by one-step,and it had higher atomic economy.5.When the reactants were liquid state,we could use Cu/MIL-101 to catalyze the A₃ coupling reaction of aldehyde,secondary amine and substituted alkyne without solvent,synthesize propynylamine derivatives in excellent yield,this reaction had the advantages of large substrate range.Conclusion:The Cu/MIL-101 had the characteristics of good morphology,stable properties and high catalytic activity.It could highly catalyze three-component reaction to synthesize 1,2,3-triazoles,1,3-butadiynes,?-ketophosphonates,pyridazines and propargylamine derivatives in higher yields.This kind of reaction has the characteristics of simple operation,environmentally friendly and strong atomic economy.