Syntheses, Structures And Catalytic Properties For Visible-Light-Driven Hydrogen Production Of Copper Or Nickel Complexes Based On Macrocyclic Oxiamido Ligands

The thesis contains of two aspects. One part is about the synsthesis of the eight mononuclear metal complexes of copper or nickel based on macrocyclic oxamide- ligands. The other part is the noble- metal- free homogeneous photocatalytic hydrogen system containing the complex CuL1 as the photo-catalyst, the xanthene organic dye as the photosensitizer and TEA as the sacrificial agent. The detailed process is as followed:1. Eight macrocyclic mononuclear complexes Cu L1, C uL2, C uL3, CuL4, N iL1, NiL2, N iL3 and N iL4 have been synsthesized with the template method. The complexes are characterized and analyzed by single-crystal X-ray diffracion analysis, ESI-MS, IR, EA, and TGA.2. We achieved in photocatalytic hydrogen production by building the homogeneous photocatalytic hydrogen system containing the comp lex Cu L1 as the catalyst, EY as the photosensitizer and TEA as the sacrificial agent in the methanol and water. Optimizing the conditions of photocatalytic hydrogen, such as the kind of and the amount of solvents, photosensitizers and sacrificial agents, t he pH value, and the amount of the catalyst. Under the optimization, the photocatalytic performance of the eight complexes have been researched and compared with the cause analysis. The study of stability of the photocatalytic system suggests that the deactivation of the system is due to both the decomposition of C uL1 and EY, and Cu L1 turns into pure copper in fact. The fluorescence quenching experiments of complexes and TEA to EY suggest that the exicited state 3*EY is mainly reduction quenched by TEA. The complex C uL1 is decomposed into C u(0) which is the real catalytic species by the mecury poisoning.