Since the end of 1980s,the research of metal-organic framework materials(MOFs)has been in the forefront of materials,chemistry,energy,physics and other disciplines,and its focus has also been developing from synthesis,structure testing,single performance research to the development of multi-functional materials and practical applications.At present,MOFs and their related materials have shown excellent performance in gas storage and separation,sensing,catalysis,photoelectricity,energy storage and other aspects.In order to give full play to the porous confining function of MOFs,MOFs based MOF composites,especially functional nanoparticles@MOF,have opened a new window for the application of MOFs materials and added new innovative vitality to the research.In this paper,starting from the design,synthesis and application function expansion of MOFs materials,we are committed to the synthesis of porous MOF crystalline materials and the construction of MOF confined composite materials,explore the application of the composite materials in heterogeneous organic catalysis and electrocatalysis.The main research content is divided into four parts:Part one:literature review,first introduced the overview of metal organic framework materials and the main classification,secondly discusses the restricted domain of metal organic framework in chemical sensing,electrocatalysis,application of chemical aspects such as heterogeneous catalysis,and representative literature reports for them,in the end,the basis of the topic selection is described.In the second part,the synthetic rule,crystal structure and related basic physicochemical properties of 13 porous MOF materials were discussed in detail.The effects of different reaction conditions and organic components on the final structure were analyzed.The 13 porous MOF crystalline materials are as follows:{(Me2NH2)l.5[Co0.75(H6L6)0.5]}n 1{Me2NH2[Co1.5(μ3-OH)(H6L1)0.5(H2O)1.5]}n 2{Co2(H6L1)(4,4’-bpy)0.5·H2O}n 3{Co1.5(H6L1)(bpe)1.5-3H2O}n 4{Co(H6L1)(2,2’-bpy)}n 5{Co3.5(μ2-OH)(H6L1)2(1,4-bib)2·5H2O}n 6{Ni0.5(H6L1)0.5(4,4’-bpy)0.5·H2O}n 7{Cu3(H6L1)(1,4-bib)3}n 8{Mn2.5(H6L1)·5H2O}n 9{Co0.5(H4L2)0.25·H2O}n 10{Co(H4L2)0.5(4,4’-bpy)0.5}n 11{Co(H4L2)0.5(bpe)0.5}n 12{Co(H4L2)0.5(1,4-bib)0.5}n 13The third part:In view of the instability of MOFs in the electrocatalytic oxygen evolution reaction(OER)under alkaline conditions,the localized composite Co-BTC@CoOOH was synthesized in situ under the condition of strong alkaline reaction,which showed good stability and good OER performance.On this basis,the effects of the composite conductive matrix and the local-limited loaded precious metal Ag on the OER properties of Co-BTC@CoOOH were explored.The effect of electrode catalyst load of Co-BTC@CoOOH on the performance of OER was investigated.The overpotential of the composite OER was 304 mV when the current density was 10 mA·cm-2 in a reasonable proportion.In addition,the screening of a classic M3(μ3-O)unit of CPM-33a porous confined load research,examines the precious metal load,different metal doping on CPM-33a framework catalytic effect the performance of methanol oxidation(MOR),found that the double metal doped greatly enhance the CPM-33a framework material itself methanol oxidation activity,CPM-33a(Ni2Fe1)area of activity of 25.83 mA·cm-2 catalyst,a single metal activity promoted twice;The confining loading of precious metal Ag enhances the methanol oxidation activity of CPM-33a(Ni),and makes the CPM-33a(Ni2Co1)without methanol oxidation activity exhibit a certain methanol oxidation performance.In the fourth part,the porous rare earth europium-based MOF(CTGU-19)synthesized by our research group in the early stage and three isomorphic porous crystalline materials 11-13 were selected as the localized carrier to carry out the localized load research:With CTGU-19 as the carrier substrate preparation of precious metals confined explore the single and double metal composite catalyst confined load on catalytic properties of nitro phenol,bimetallic confined composite catalyst on the nitro phenol showed good catalytic activity,Ag0.8Au0.2@CTGU-19 of 2-NP,3-NP and 4-NP unit mass reduction rate constant were 68.8,53.80,and 52.34 s-1·g-1,and analyzes catalytic mechanism.In homogeneous porous crystalline material 11-13 confined load different precious metals(Ag,Au,Pd,Ru),to explore the load precious metal type,porous morphology,hole size effect on the performance of the composite catalytic nitro phenol,found three types of confined composite materials in the smaller size,load of precious metal atomic radius is relatively small,high catalytic activity,The reduction activity of the confined composite catalyst Ru@{Co(H4L2)0.5(4,4’-bpy)0.5}n(crystalline material 11)loaded with precious metal Ru on 4-NP reached 50.72 s-1·g-1The fifth part:summarize and look forward to the overall work of the paper. |