Design,Synthesis,Gas Separation And Electrical Properties Of Metal-Organic Framework Based On N-Containing Ligand

Metal-organic framework(MOF)are an emerging class of porous materials with potential applications in gas storage,separations,catalysis,and conductivity due to large specific surface area,good chemical stability,adjustable pore size and high crystallinity,which has very high research value.In this thesis,a series of nitrogen-containing organic ligands were designed,synthesized,and coordinated with metal ions to form two-dimensional or three-dimensional metal-organic framework materials.Through characterization and related tests,the relationship between the unique structure and properties was studied and the applications in gas separation and electricity were explored.The main research content consists of three parts:First,the nitrogen-containing organic ligand TMBP was synthesized and coordinated with Cu X(X=I,Br,Cl)to form three ultra-microporous metal-organic framework TCu X(X=I,Br,Cl),which have the same structure.The pure gas adsorption isotherms for C₂H₂and CO₂ were studied and the binding sites were determined.The separation selectivity for C₂H₂over CO₂ was studied by IAST and dynamic breakthrough experiments.The results show that the separation selectivity of TCu X for C₂H₂over CO₂ is in the forefront compared with similar adsorbents,and the performance of TCu Cl is the best in TCu X,which can be attributed to a new type of strong binding site for C₂H₂,which also namely H-C?C-H…X interaction.Then,the organic linker H₂DPA featuring the large?-system of anthracene coupled with two pyrazolyl groups was designed,synthesized,and coordinated with Ag₂O to form metal-organic framework Ag₂(DPA).Through the single crystal test and analysis,it can be found that Ag₂(DPA)has unique structure and conjoin the four forces of face-to-face interaction,argentophilic interaction,Ag(I)-?interaction and Ag(I)-pyrazolate bonding to promote intermolecular interactions both within and across the layers.The unique structure and electronic interaction were also revealed by the red shift of photoemission spectra and the significant reduction of the electronic band edge as determined by diffuse reflectance spectroscopy.Finally,the nitrogen-containing and sulfur-functional molecule L1 with large?-conjugated aromatic systems was designed and synthesized.The sulfur-containing side chain of L1 was hydrolyzed to thiol by in-situ hydrolysis and coordinated with copper ions to form metal-organic framework HATN-Cu.The nitrogen-rich MOF with large?-conjugated aromatic systems is beneficial to the electrical properties of the material,so the electrical properties of the material was studied.The conductivity of this material is 1.02×10^-8 S/cm,and the overpotential to HER at current density of 10 m A/cm² is 602 m V.The structure of material can be adjusted later to improve its electrical performance.