The Preparation Of Composites Based On Ruthenium Carboxylic Bipyridine Carbonyl Complexes And Its Application In Photocatalysis

Ruthenium complexes are one of the class of conventional homogeneous catalysts that are most concerned because of the type of their catalytic reaction is diverse, catalytic efficiency is high, the structure can be modulated and their mechanisms can be investigated at the molecular level. Ru carbonyl complexes are well photosensitizer and homogeneous catalysts. Thus preparing the Ru carbonyl complexes based composites to construct novel photocatalysts so as to provide the necessary chemicals as well as solve environment issue like green house effect is significant.This thesis consists of two parts. The first part is about The establish of Ru carbonyl complexes and CdS hybrid system, and study the hydrogenation of ketone under visible light. By synthesis of a series of ruthenium carbonyl complexes, among which Ru(5,5’-dcbpy)(CO)2Cl2 and [Ru(4,4’-dcbpy)2(CO)Cl]Cl are two unreported complexes. They were applied in the hydrogenation of ketone under visible light with water as solvent, triethanolamine as sacrificial agent, It was found that Ru carbonyl complexes was deprotonated under basic conditions and a strong interaction between positively charged CdS thus facilitate the electron transfer between themselves. An efficient photocatalytic system was built on the hydrogenation of ketone over CdS/Ru carbonyl complexes.Although the photocatalytic system on the hydrogenation of ketone over CdS/Ru carbonyl complexes is efficient. The ruthenium complexes are easily lost and difficult to recycle. Graphene oxide was used as a basement, the Ru(4, 4’-dcbpy)(CO)2(CF3SO3)2 was fixed on it by post-synthesis method. CdS/RGO-Ru photocatalytic system was built successfully though the activity of hydrogenation of ketone declined a little, the recovery is greatly improved.The second part is about bifunctional MOF-253 for construction of a series of MOF-253-Ru as active and robust visible-light-responsive photocatalyst for CO2 reduction. MOF-253 with the N, N vacancies thus can be used as a ligand and a basement, which was reacted with ruthenium complexes to construct MOF-253-Ru photocatalytic system, and apply them in CO2 reduction under visible light with CH3CN as solvent and triethanolamine as sacrificial agent. It was found that it behaves well when the content of ruthenium complexes at 6% to 10%.While similar complexes like Ru(5,5’-dcbpy)(CO)2Cl2, Ru(4,4’-dcbpy)3Cl2 and Ru(5, 5’-dcbpy)3Cl2 almost do not take effect. What’s more, By using Ru(5, 5’-dcbpy)(CO)2Cl2 partially substituted ligand 5,5’-dcbpy, and AlCl3*6H2O as metal salt, a MOFs named MOF-I MOF-II with the same configuration of the MOF-253 was prepared, and they can reduction of CO2 under visible light. A mechanism of reduction of CO2 over MOF-253-Ru photocatalytic system was proposed:CO or bipyridine on the ruthenium complexes was released and leave the space under visible light irradiation, and CO2 attack Ru center with the aid of TEOA affording electron and proton, the formic acid generated.