The Design,Synthesis And Functionalization Of Covalent Organic Framework Based On Anthracene And Naphthalene Derivativess

Covalent organic frameworks(COFs)is a new kind of crystalline porous materials,which is composed of light elements(usually C,H,O,N and B).It is connected by covalent bonds,and has a clear topological structure.Because of their permanent porosity,high specific surface area,open pores,adjustable framework and excellent thermal and chemical stability,they are used in various applications(such as heterogeneous catalysis,adsorption and separation,drug delivery,sensing and energy storage,etc.)and have good application prospects.However,up to now,most of the reports on COFs focus on2D-COFs,while the development of functionalized 3D-COFs is relatively slow,so the reports on functionalized 3D-COFs are relatively rare.The reason why the development of functional 3D-COFs is relatively slow is that the design and synthesis of 3D-COFs are more difficult compared with 2D-COFs.The synthesis of 3D-COFs requires rigid building units with three-dimensional structure,while it is difficult to form high crystallinity materials with using this type of building units,especially the functional three-dimensional building units in general.Moreover,3D-COFs is easy to form interpenetrating structure,which makes its pore size smaller and its application limited.In a word,the structure and crystallinity of 3D-COF will be destroyed in the process of functionalization.Therefore,the reasonable design of stereoscopic building units and COFs structure and the reasonable selection of functional methods and conditions are very significant for the development of functional 3D-COFs.To sum up,this paper designs two functionalized 3D-COF based on anthracene and naphthalene derivatives,and uses the inherent characteristics of its skeleton to realize its reversible combination with singlet oxygen,and then realizes its in-situ functionalization.This paper mainly includes the following aspects:The first part: Firstly,we introduce the history of COF materials;secondly,we introduce the synthesis methods and reaction types of COF;then we introduce the current COF functionalization methods and their application areas;finally,the meaning of the topic of this thesis is introduced.Part 2: First,we introduced two organic building blocks based on anthracene and naphthalene derivatives,9,10-bis(4-formylphenyl)anthracene(DAPHA)and1,4-bis(4-methyl)Acylphenyl)naphthalene(DAPHN)synthesis in detail;second,we synthesized two COF materials by solvothermal method through these two building units and tetrakis(4-aminophenyl)methane(TAPM): JUC-575 and JUC-576;Finally,we tested and characterized the structure,morphology and stability of these two materials.The third part: First,we first introduce the application,characteristics and sources of singlet oxygen in many fields;then we make JUC-575 and JUC-576 combine with singlet oxygen to form the corresponding EPO-COF by using the photooxidation reaction.In addition,the EPO-COF was characterized;then the EPO-COF was reduced to the original parent COF through the photoreduction reaction.Finally,we carried out the cycle test and quantitative analysis,and explained its application prospects.The fourth part: We summarize the content of this article and look forward to the future prospects of COF materials.