Systhesis Of Electrocatalytic Performance Of Fluorophdiyne

Graphdiyne(GDY)is a carbon material with independent intellectual property rights of China,and Chinese scientists have led this research field internationally.Graphdiyne is the first new two-dimensional carbon material composed of sp2 and sp hybridized carbon.It has many unique properties such as natural pore structure,rich carbon chemical bonds,natural band gap,excellent mechanical and chemical stability,and so on.Since being first successfully synthesized chemically in large areas by academician Li Yuliang of the Institute of Chemistry,Chinese Academy of Sciences in 2010,graphdiyne has shown great potential and wide prospects in many fields such as catalysis,energy,and electronics.In this thesis,graphdiyne is prepared by a method of controlled substitution and modification,and fluorine-substituted graphdiyne is prepared,which realizes the precise control of the structure of graphdiyne and introduces a new catalytic activity center to solve the difficulty of traditional metal-free catalyst such as poor catalytic selectivity and activity,and stability.The as-prepared catalyst were successfully used in overall water-splitting reaction and ammonia synthesis reaction under room temperature and atmospheric pressure.The catalyst showed high reaction selectivity,catalytic activity and stability.Moreover,corresponding catalytic mechanism was further studied with the combined theoretical study.This paper mainly includes the following parts:The first chapter is the development history of graphdiyne.Starting from the unique electronic and chemical structure of graphdiyne,the basic properties of graphdiyne are elaborated,the synthesis and functional modification methods of graphyne are introduced,and the important research achievements made by graphdiyne in catalysis,energy conversion and storage are outlined,showing the broad application prospects of graphyne.In the second chapter,a bottom-up method was used tfor the in-situ growth of a fluorographdiyne filmon a three-dimensional carbon cloth substrate.We then characterized its structure and morphology in detail and used it as the first metal-free catalyst for electrochemical overall water splitting.Theoretical calculation results show that the introduction of fluorine atoms changes the electronic structure around the C2 atom and enhances its ability to adsorb reaction intermediates,thereby enhancing its reactivity;experimental results show that the material has excellent electrocatalytic total hydrolysis reaction activity and stability in both acidic and basic conditions.In the third chapter,the single crystal fluorographdiyne was successfully synthesized by the method of interface induction,and it was successfully applied to the synthesis of ammonia at room temperature atmospheric pressure for the first time.We have proved for the first time through experiments and computer simulations that single crystal fluorographdiyne has a 9-fold ABC stacking structure.At the same time,as a metal-free catalyst,crystalline fluorine-substituted graphdiyne exhibits excellent ability to reduce nitrogen to ammonia,and the results illustrated high reaction selectivity,high ammonia yield and high Faraday efficiency of crystal fluorographdiyne under neutral conditions.In the fourth chapter the development of graphdiyne is summarized and prospected.