Preparation Of Fullerene/Graphene Nanohybrid Materials And Their Application In Electro-catalysis

Recently,carbon nano-materials have attracted wide attention because of their excellent electrical,thermal and mechanical properties.Carbon materials,containing carbon black,fullerene(C₆₀),carbon nanotubes（CNTs）,graphene and so on,have been demonstrated to exploit advantage of the merit of each member,and further study some synergistic and catalytic performance for their hybrid materials.In this thesis,two nano-hybrid materials have been prepared by different interaction between fullerene and graphene,and further used as support for immobilization of Pd nanoparticles to prepare Pd/(rGO/C₆₀-pyrro)and Pd/(rGO/C₆₀-NH₂)catalysts for direct methanol fuel cells（DMFC）.（Ⅰ）Fullerene derivatives of multi-substituted pyridine class were synthesized through Prato reaction.The strong hydrogen-bond/electrostatic interaction between GO and fulleropyrrolidines derivatives(C₆₀-pyrro)produces a self-assembled GO/C₆₀-pyrro composites,in which C₆₀-pyrro units intervene to form supports with abundant ripples and wrinkles.By varying the ratio of GO to C₆₀-pyrro,the GO/C₆₀-pyrro（4:1）have an optimized compart and stable structure,Pd nanoparticles are uniformly distributed on the support(GO/C₆₀-pyrro).（Ⅱ）Amine functionalized-fullerene derivatives(C₆₀-NH₂)were reduced from nitro functionalized-fullerene derivatives(C₆₀-NO₂)which were synthesized through Prato reaction by Stannous chloride dihydrate（SnCl₂·2H₂O）as reducing agent.A new type of nano-hybrid materials were prepared by the chemical bonding of epoxide groups of GO with amino groups of C₆₀-NH₂,which substantially enlarged the interlayer spacing of GO sheets and effectively prevented the aggregation after reduction,furthermore,provided a large accessible surface area for better dispersing Pd nanoparticles.The Pd/(rGO/C₆₀-NH₂)catalysts were co-reduced with Pd precursor by sodium borohydride（NaBH₄）as reducing agent.The electrocatalytical performances of as-prepared Pd/(rGO/C₆₀-pyrro)and Pd/(rGO/C₆₀-NH₂)catalysts were tested for methanol oxidation reactions（MOR）under the alkaline media.The result shown that the activity and stability for methanol oxidation were significantly enhanced which was ascribe to the synergistic effect between GO and C₆₀.