Organic Semiconductors Based On Peryleneimide:Design,Synthesis And Applications Of Artificial Photosynthesis

Converting solar energy into chemical hydrogen energy by artificial photosynthesis system is a promising way to solve the energy crisis.Since 1970s,inorganic semiconductors and C3N4 polymers are the research focus of artificial hydrogen production in photosynthesis,and a large amount of literature has been published.However,the quantity constraints and low visible light utilization of inorganic semiconductors hinders their developments.Most of the metal organic complexes and organic small molecules are easily decomposed by the solar light,making them extremely limited in practical applications.Therefore,the development of chemically stable ?-conjugated organic semiconductor photocatalysts and the design of artificial photosynthesis systems are one of the main directions for the development.In this dissertation,the peryleneimide derivatives were studied,we synthesis the peryleneimide derivatives as photosensitizers or photocatalysts for artificial photosynthesis systems and explore the relationship between structures,bandgaps and profermances.Three artificial photosynthesis hydrogen production systems:(1)[PMI-COOH]n-(PVP-Pt),[PMI-COOH]n is an organic semiconductor photosensitizers by the self-assembly of N-hexylcarboxylic acid-3,4-peryleneimide;(2)[PMI-K]n-PVP-Pt,[PMI-K]n is an organic semiconductor photosensitizer formed by the self-assembly of N-lysine-3,4-peryleneimide;(3)[PMI-COOH]n-(DuBois Ni-NH3+),DuBois Ni-NH3+ is a water-soluble positively charged DuBois Ni(simula iron hydrogenase).Four photocatalytically activated oxygen systems:(1)[PMI-COOH]n;(2)[PMI-K]n;(3)[PDI-COOH]n,[PDI-COOH]n is an organic semiconductor photocatalyst formed by the self-assembly of N,N'-dihexylcarboxylic acid-3,4,9,10-peryleneimide;(4)[PDI-K]n,[PDI-K]n is an organic semiconductor photocatalyst formed by the self-assembly of N,N'-double lysine-3,4,9,10-peryleneimide.The paper has obtained the following innovative results and conclusions:(1)PMI-COOH and PMI-K are small molecules in DMSO and self-assemble in water to form nanoplatelets[PMI-COOH]n and[PMI-K]n.These artificial photosynthesis system were constructed with[PMI-COOH]n or[PMI-K]n as photosensitizers,PVP-Pt or DuBois Ni-NH3+ as catalysts,and ascorbic acid as sacrificial agent.After 5 h of light irradiation,the hydrogen production activity of these systems were 20.2 mmol/g,5.1 mmol/g,and 10.4 mmol/g,respectively.They were still stable after light irradiation for 20 h.The main product of[PMI-COOH]n and[PMI-K]n activated oxygen is 102.(2)PDI-COOH and PDI-K are small molecules in DMSO and self-assemble in water to form nanoplatelets[PDI-COOH]n and nanowires[PDI-K]n.The main product of[PDI-COOH]n activated oxygen is 1O2,while the main product of[PDI-K]n is ·O2-.These experimental results show that the peryleneimide derivatives can self-assemble to form photothermally stable organic semiconductors through ?-?interactions,hydrogen bonds and etc.The artificial photosynthesis hydrogen production system constructed by using them as photosensitizers,which show efficient and stable hydrogen production.And this type of organic semiconductor had a good ability to activate oxygen.These results have important guiding significance for the design of an efficient artificial photosynthesis system in the future.