Study On Formation Reaction Of C-N Bond Catalyzed By Transition Metals And Its Application

The C-N bond is one of the most abundant chemical bonds and widely used in many biological macromolecules and organic molecules.Nitrogen-containing compounds with C-N bonds are of great significance in scientific research,industrial applications and so on.Therefore,efficient synthesis of carbon-nitrogen bonds has considerable scientific potential.The main work of this paper is that C-N bond formation catalyzed by transition metal to prepare nitrogen-containing compounds,such as 1,3,5-s-triazine derivatives,nitrogen-containing functional polyhedral cage complexes and N-doped porous carbon material.The carbon material applied widely in dye adsorption(rhodamine B,Alizarin Yellow R,methyl orange)and used as NIR-driven photocatalyst for H2 evolution.The main work mainly starts from the following aspects:1 The 1,3,5-s-triazines contain ?-conjugated systems that make it highly electron-defective and spatially coplanar,and thus become a key area of chemical research,and have also been used in high thermal stability materials,optical materials,surfactants,dyes,pharmaceuticals and textiles,etc.Therefore,we will focus on the study of the preparation of 1,3,5-s-triazine-based single crystal samples under mild reaction conditions using readily available raw materials.It has been found that the cyclotrimerization of acetonitrile and benzonitrile catalyzed by TiCl4 as a Lewis acid catalyst can successfully prepare 1,3,5-s-triazine derivatives with C-N bonds(acetonitrile polymers[(CH3)3C3N3]and benzonitrile polymer[(C6H6)3C3N3]compounds)under solvothermal reaction conditions.Furthermore,single crystal samples were obtained.The single crystal X-ray diffraction characterization confirmed that both 1,3,5-s-triazine derivatives have a C3N3 hexatomic ring structure.2 The functional polyhedral cage-like complexes have tunable structures,host-guest chemistry etc.,and have been used in catalysis,chemical sensors,and molecular recognition.However,due to the high sensitivity of titanium precursors in air,the preparation and application of titanium cage-like materials with C-N bonds are limited.Therefore,we will be devoted to systematically study the synthesis methods,functional properties of titanium-based cage with C-N bonds.Titanium-based cage with a single crystal structure can be successfully prepared via a one-pot solvothermal reaction and characterized in detail.It was found that the synthetic process of the Ti-based cage involves the cascade formation of covalent and coordination bonds,in which TiCl4 functions as the Lewis acid catalyst for the acylation condensation reaction,and then as the coordination center for Ti-based cage assembly.For the first time,this cascade reaction from the field of organic synthesis was applied to the synthesis of a coordination compound.Benefiting from high efficiency and low cost,the application of the cascade reaction could pave a new way for coordination compound synthesis.3 Nanoporous carbon materials are receiving great research interest in both academia and industry owing to their high porosity,tunable pore sizes,low costs,and hence promising applications in water purification,as catalyst supports,and as electrode materials in supercapacitors.Combined with previous research experience and relevant knowledge that nitrogen-doped carbon materials have improved reaction performance,mechanical properties,and catalytic properties,we will focus on the preparation of nitrogen-doped porous carbon materials with C-N bonds.It has been found that a N-doped porous carbon material was synthesized successfully by the one-step direct heating of dicyanobenzene in the presence ZnCl2,free from any other treatment.The resulting NPC-1000 sample structurally features graphite-like monolayers with thicknesses of approximately 1.4 nm and possesses a high specific surface area and a narrow pore-size distribution.This material exhibits potential gas-storage capabilities with a H2 uptake of 2.96 wt%at 77 K and a CO2 uptake of 23.4 wt%at 278 K and 0.1 MPa.NPC-1000 is near-IR photoactive and shows a pronounced photothermal effect.We demonstrated the first example of the use of a carbon material(NPC-1000)as a nearIR-driven photocatalyst for H2 evolution.The results imply that a cheap precursor,a facile synthesis procedure,and efficient near-IR absorption will stimulate the use of N-doped porous carbon materials as full solar spectrum photocatalysts for H2 evolution.Precise regulation of the N content,pore sizes,and the carbon texture is currently under investigation to enhance the performance further.