Design,Preparation And Studies Of Iron,Cobalt,Nickel And Molybdenum Complexes With Electrochemical Hydrogen Production Or Magnetic Properties

With the development of economy and society,human consumption on energy is increasing highly.Traditional fossil fuels,like coal and petroleum,which human beings survive on are face to dry up because of their non-renewable with in short time.At the same time,the gases produced by combustion such as CO2,SO2 and NOX can seriously damage the atmosphere even lead to global warming and acid rain.As a result,people presently focus on finding renewable and cleaner energy?eg.solar,wind and tidal energy?.However,as those energy acquisitions are regional restrictions and the energy storage is inconvenient,it is only suitable for using in specific region.At present,hydrogen energy is one of the resource that most likely to replace traditional fuel.As H₂ can be obtained by electrolysis of water,available raw materials are one of the greatest advantages of hydrogen energy.Meanwhile,water is the only combustion of H₂,which means the zero-polluted to the environment.It is a cycle process of electrolysis of hydrogen?energy storage?and hydrogen combustion?energy supply?.That is to say,the utilization rates of hydrogen atoms are up to 100%.Electrolysis of water is the most convenient and effective method for hydrogen preparation.And the catalyst is added to increase the rate and efficiency of hydrogen production in order to reduce energy consumption.Therefore,design,preparation and application of complex like small molecule catalysts have become a hot research topic to the science researchers.Based on the investigation of the related literature,it is found that the catalytic performance of the complexes can be exchanged by difference ligand structure and central metals.Therefore,this paper mainly completed the following research work:1)Preparation of four organic ligands,2-pyridylaminomethyl-N,N-bis?2-methylene-4,6-bitertbutylphenol??H₂L'?,2-tetrahydrofuranylaminomethyl-N,N-bis?2-methylene-6-tertbutylphenol??H₂L3?,2-tetrahydrofuranylaminomethyl-N,N-bis?2-methylene-4,6-bimethylphenol??H₂L4?and 2-tetrahydrofuranylaminomethyl-N,N-bis?2-methylene-4,6-bifluorophenol??H₂L₅?.2)Preparation and characterization of five complexes: [Mo?L'?O2?]1,[Ni^??bpy?3]?PCPP?22,[Fe^?L3Cl]3,[Co^?₂L₄]4,and [Co?2L₅]5.3)Electrochemical studies show that totally five complexes have electrocatalytic performance for hydrogen generation both from organic acid and water.TOF?turnover frequency?values of the complexes in the buffer solution of pH 7.0 were 373.1 h-1?1,overpotential 787.6 mV?,1464 h-1?2,overpotential 837.6 mV?,110.9 h-1?3,overpotential 937.6 mV?,243.0 h-1?4,overpotential 887.6 mV?and 159.8 h-1?5,overpotential 837.6 mV?.What's more,the magnetic properties were tested because of magnetic interactions between CoII ions in both complexes 4 and 5 with organic ligands H₂L4 and H₂L₅.4)Preliminary inference of catalytic mechanism has been researched.