Design,Synthesis And Application Of Functional Ferrocene Derivatives

Ferrocene was discovered in the middle of the 20th century,and received much attention owing to its unique sandwich structure and excellent redox properties.In this paper,a series of ferrocene derivatives were synthesized,including ferrocene-containing hyperbranched polymers and ferrocene-based heterobimetallic complexes.With regards to the characteristics of the obtained materials,the applicable potential in lithium ion batteries(LIBs),environmental treatment and electrocatalysis have been studied,respectively.The main contents are described as follows:1. The hyperbranched polymer(P-Fc FTEPA)containing a ferrocene side chain modification was synthesized by the cross-coupling reaction of ferrocene-modified diiodofluorene and alkynyl-functionalized triphenylamine.Then the structure,morphology and elements,etc,have been characterized in detail.The obtained polymer has a uniform spherical structure and can be used as a negative electrode active material in LIBs.The charge-discharge performance was kept stable over 200 cycles at the current density of 100 m A g^-1,the coulombic efficiency was stable at about 97%,the specific discharge capacity reached as high as 755.2m Ah g^-1,and which indicated the high capacity performance and good cycle stability.In addition,the charge-discharge properties performed at different current densities revealed its good rate performance.2. ZIF-67s were introduced to control the morphology of hyperbranched polymers during the polymerization of P-Fc FTEPA,and the resulting polymer showed the uniform polyhedrons with hollow structure.Both spherical and polyhedral polymers were used as precursors to provide carbon and iron sources,respectively.The precursors were pyrolyzed under an inert atmosphere of N₂ to prepare porous carbon materials,in which Fe-based nanoparticles were evenly dispersed.The morphology,element distribution,magnetic properties,specific surface area and pore size distribution were fully characterized.The specific surface area of the carbon material prepared from the hollow polymer(P-Fc FTEPA-H)was increased sharply compared with that synthesized from the solid sphere polymer(P-Fc FTEPA)(1195 m² g^-1 vs.417 m² g^-1).The obtained carbon material was used for the removal of pollutants in water,and the saturated adsorptive amount of heavy metal Pb(II)ions and organic dye rhodamine B reached30.5 mg g^-1 and 28.14 mg g^-1,respectively.The adsorbent can be easily recycled by the external magnetic field of magnetic bar,which greatly reduces the energy consumption for separation and shows a great potential in removing the trace amount of heavy metal ions and organic pollutants in water.3. A ferrocene-functionalized heterobimetallic complex((Fc TPy)Pt OAc)was designed and synthesized.The complexes were used as single-source precursors to produce Fe Pt alloy nanoparticles by direct pyrolysis under an Ar/H₂ mixed atmosphere.The structure of the precursor and the morphology,element distribution,and phase of the Fe Pt nanoparticles were studied in detail.The obtained Fe Pt nanoparticles showed highly efficient catalytic activity for hydrogen evolution reaction(HER)and oxygen reduction reaction(ORR),which were superior to comprehensive performance of commercial Pt/C catalysts.In addition,the bimetallic complexes were further modified on the side chain of the hollow structure hyperbranched polymers(P-(Fc TPy)Pt TPA)and then the polymers were used as single-source precursors to obtain L1₀-Fe Pt nanoparticles supported on porous carbon materials.The resultant nanomaterials also showed good catalytic activity in ORR as commercial Pt/C catalysts,indicating that Fe Pt nanoparticles prepared by one-pot pyrolysis of metal polymer precursors have good potential in electrocatalytic applications.