서강대학교

초록/요약

This thesis concerns the development of water oxidation with [Ru(bpy)3]3+: and its mechanism during light driven reaction which are the essential components for solar energy conversion to fuels . By oxidizing water (with high pH and reaction rate increase with increasing the pH) [Ru(bpy)3]3+ gives oxygen. To create OH• radical which is one electron process from water on the presence of [Ru(bpy)3]3+ and OH• dimerizes to H2O2. This H2O2 is oxidized to O2 and then also [Ru(bpy)3]2+ recovered. The oxidation of water by [Ru(bpy)3]2+ and S2O82- light reaction without adding any other extra catalyst was produce significant amount of O2 from water .Catalytic mechanism are thoroughly investigated by chemical and kinetic study. A blue dimer (well known water oxidation catalyst) was used together with [Ru(bpy)3]2+ - S2O82- system and it produced 10 times higher O2 yield. Photochemical water oxidation was demonstrated successfully using Ru-based catalyst. We also prove that the original oxidation catalysts insight reaction solution is sulfate bonded and oxygen bridging dinuclear ruthenium complex here we termed as orange dimer because of its color. This triclinic crystal structure of orange dimer is not symmetric like monoclinic blue dimer and have the higher oxidation state. First time crystal structure analysis of this orange dimer was done in this thesis to know the actual active site of the catalyst. In This thesis first time demonstrated reservoir type Mo based POM which can prolonged reaction time by longer than without using POM. This Mo based POM can make complex with [Ru(bpy)3]2+. Holding [Ru(bpy)3]2+ and release [Ru(bpy)3]2+ slowly with time which can act insight reaction during water oxidation. By using Mo - based POM which can make long live of [Ru(bpy)3]2+ and so water oxidation go for long time and total O2 produced is ~5 times higher than without using Mo based POM.