Synthesis And Photocatalytic Hydrogen Production Of Photosensitive Cd-MOF And Fluorescence Recognition Of Pt Based Supramolecules

Coordination polymers（CPs）have developed rapidly and become an important research direction in many branches of chemistry,such as organic chemistry and inorganic chemistry.Porous CPs,called metal-organic frameworks（MOFs）,are widely used in the fields of gas adsorption,separation and catalysis due to their outstanding pore structure and stable frame structure.In this thesis,the adsorption and separation properties of Cd-MOF on nitrogen-containing five-membered heterocyclic molecules were studied,and one new type of photosensitive Cd-MOF materials were constructed based on the remarkable color change of the host-guest systems.The effect of the photosensitive Cd-MOFs on the hydrogen production photocatalyzed by[FeFe]-hydrogenase and TiO₂was explored.Two new crown ether-appended tetraplatinum（Ⅱ）macrocyles were synthesized and used for chemosensor for cation detection.Ⅰ.The single-component adsorption and competitive adsorption and separation of pyrrole and its methyl-substituted derivatives of Cd-MOF were studied.The phenomenon of"supersaturation"adsorption was found during the adsorption of pyrrole,which made the unit cell of frameworks change from 5400 to 5900（?）³.In the competitive adsorption process,it was found that the selective adsorption order of Cd-MOF for pyrrole and its methyl-substituted derivatives was:pyrrole>N-methylpyrrole>2-methylpyrrole>3-methylpyrrole.Ⅱ.It was found that Cd-MOF（?）guest with different colors had different effects on the efficiency and volume of hydrogen production of catalyzers 1 and 2 photocatalyzed by[FeFe]-hydrogenase and TiO₂.The experimental results showed that all of the photosensitive host-guest systems promoted photocatalytic hydrogen production.For catalyzer 1,photosensitizer Cd-MOF（?）3Pyrrole has the greatest promotion effect on hydrogen production;for catalyzer 2,photosensitizer Cd-MOF（?）（3-Methylpyrrol）has the best promotion effect on hydrogen production,for TiO₂,photosensitizer Cd-MOF（?）3pyrrol has the best promotion effect on hydrogen production.Ⅲ.Two new crown ether-appended tetraplatinum（Ⅱ）macrocyles（Pt1 and Pt2）were synthesized from the linear di-carboxylate ligands and dinuclear Pt（Ⅱ）complexes.It was found that Pt1 has the best selectivity for alkali metal Na⁺,while Pt2 can selectively recognize alkali earth metal Mg²⁺.In summary,in this thesis we have studied i)the adsorption and separation properties of Cd-MOF for nitrogen-containing five-membered heterocyclic small molecules;ii)the effect of photosensitive Cd-MOF（?）guest systems on the hydrogen evolution catalyzed by[FeFe]-hydrogenase and TiO₂;iii)the synthesis and property of crown ether-appended tetraplatinum（Ⅱ）macrocylic chemosensor for cation detection.