| Photocatalysis,a research subject related to multiple fields of chemistry,is of importance for not only the fundamental science,but also the industrial application.For example,photosynthesis in nature uses carbon dioxide and water as the reactants to produce carbonhydrates via a sun light-drived enzyme catalized process.The man-made photosensitizers have strong redox ability under light irradiation,which can be applied to photocatalytic organic syntheses and redox conversion of inorganic substances,providing a promising way for solar energy acquisition and storage.Photocatalytic reactions have been widely studied in air purification,water purification,sterilization and deodorization,antifouling and antifogging.Metal-organic frameworks(MOFs)have drawn great attention in many research fields due to their properties of uniform pore size and high specific surface area.In particular,the development of MOFs with photocatalytic performance has being the focus of researchers in the field of photocatalysis.In this theis work,three tripyridine ruthenium complex photosensitizers with bi-or tri-carboxylates substituents have been designed and synthesized.Combined with copper or lanthanide metal ions as nodes,the Ru complexes were applied as linkers to construct a series of new metal-organic frameworks via solvothermal methods.These MOFs are featured with photosensitive linkers and potential catalytic activity nodes,and their photo-chemical/catalytic performance were investgated.The main content includes the following three sections:(1)Bis-4?-carboxy-2,2?:6?,2??-terpyridine[Ru?(tpy COOH)2](PF6-)2,and tri-carboxy2,2?:6?,2??-terpyridine[Ru?(tpy COOH)(tpy(COOH)2)](PF6-)2and[Ru?(ben-tpy COOH)(tpy(COOH)2)](PF6-)2 complexes were designed and synthesized as linkers for the construction of MOFs.In the visible light absorption region,polypyridyl ruthenium complexes are classic photosensitizers due to their unique HOMO/LUMO levels and long-lived excited states.(2)One-dimensional,two-dimensional and three-dimensional metal organic frameworks were synthesized using bis-/tri-carboxylate Ru photosensitizers[Ru?(tpy COOH)2](PF6-)2 and[Ru?(tpy COOH)(tpy(COOH)2)](PF6-)2 as linkers and Cu2+ion as a node.The Cu node in the1D MOF Cu-MOF-Ru(tpy COO-)(tpy(COO-)2)-1D(Cu-Ru-1D)adopts a five coordination mode with triangular double-conical configurations.The Cu node of the 2D MOF Cu-MOF-Ru(tpy COO-)(tpy(COO-)2)-Cl(Cu-Ru-Cl)has a tetrahedral configuration.The orther 2D MOF Cu-MOF-Ru(tpy COO-)(tpy(COO-)2)-3Cu(Cu-Ru-3Cu)contains a three-kernel Cu cluster node,of which Cu ions are connected as three deformed coordination tetrahedra.The Cu node in the 3D MOF Cu-MOF-Ru(tpy COO-)(tpy(COO-)2)-3D(Cu-Ru-3D)adopts a four-coordination mode with a deformed tetrahedral configuration.The orther 3D MOF Cu-MOF-Ru(tpy COO-)2(Cu-Ru)contains dual Cu core The photocatalytic hydrogen production activity of Cu-Ru was assessed,which produced 35.11?mol hydrogen per gram in 240 min with an initial rate of 151.20?mol g-1·h-1 in the first hour.(3)A series of three-dimensional MOFs with the bis-4?-carboxy-2,2?:6?,2??-terpyridine Ru photosensitizer[Ru?(tpy COOH)2](PF6-)2 as the linker and lanthanide metal ions(Nd,Sm,Eu,Tb,Dy,Er,Yb)as nodes were prepared.The Ln nodes of these MOFs show two coordination configirations,mononuclear nine coordination and mononuclear eight coordination.It is found that Lanthanide metals MOFs has absorption in the wavelength range of 250-800 nm,while Yb-Ru has characteristic emission peaks of the Yb metal ions in the near infrared.A energy transfer process from the excited Ru complex linker to the Ye node was thus proposed. |
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