Assembly Of Noble Metal Nanoparticles On The Microspheres Incorporating Chlorinated Carbon Clusters (C₁₂Cl₈, C₁₆Cl₁₀) And Their Properties Of Catalysis And Absorption

In order to capture the fragments relevant to fullerene and labile fullerene isomers for understanding the mechanism of fullerenes formation,chlorines were introduced into the synthesis of fullerenes by our group.A series of chlorinated carbon clusters that could be considered as the fragments relevant to fullerene stabilized by chlorines were successfully synthesized,separated and characterilized during recent years.Based on the research on the chemical properties of chlorinated carbon clusters,the functionalization of chlorinated carbon clusters continue to emerge.However,the developments in the application of chlorinated-carbon-clusters-based functional material are not on par with the progress in functionalization of the chlorinated carbon clusters.In order to expand the applied research of chlorinated carbon clusters,the application of chlorinated-carbon-clusters-based functional materials is proposed as the research theme in my thesis.In this thesis,our research focuses on three main fields including: synthesis of the chlorinated carbon clusters,synthesis of functional materials based on chlorinated carbon clusters,and application of these functional materials.Major results have been summarized as follow:(1) By using the PCl₅ or "BMC"(a mixture of AlCl₃,S₂Cl₂ and SO₂Cl₂) as chloridizing reagent,two chlorinated carbon clusters compounds,that is,C₁₆Cl₁₀ (perchlorinated fluoranthene) and C₁₂Cl₈(perchlorinated acenaphthene) were successfully obtained by chemical synthesis.Based on the Williamson reaction of chlorinated carbon clusters,a series of chlorinated carbon clusters microspheres with uniform size were successfully obtained via a solvothermal Williamson reaction starting from chlorinated carbon clusters(C₁₆Cl₁₀ or C₁₂Cl₈) and disodium salt of dimercapto compounds(2,5-dimercapto-1,3,4-thiadizaole or sodium sulfide). Repeatedly washing of the chlorinated carbon clusters microsphere with diluted hydrochloric acid solution could facilely transform the－SNa on the surface of the microspheres into the－SH.Such thiol functionalization procedure is very useful for further applications of chlorinated carbon clusters microspheres.(2) Based on the strong complexation between noble metal and thiol groups,the thiol functional chlorinated carbon clusters microspheres that could stabilizes the noble metal nanoparticles on their surfaces is a potential supporter for noble metal catalyst.The chlorinated carbon clusters coating with Au nanoparticles(about 15 nm in size) could be facilely obtained by submerging the microspheres in the solution of HAuCl₄/sodium citrate/sodium borohydride.We used the Au/microspheres as the catalyst for reduction of 4-nitrophenol.And the result shows that Au/microspheres can be successfully recycled and reused in eight successive reactions,with a conversion rate over 90%.For comparison,unloaded Au nanoparticles were also used as the catalyst for the same reaction,whereas the conversion of 4-nitrophenol drops rapidly after only two cycles.By the same procedures,the Pd nanoparticles (about 10 nm in size) could be facilely stabilized on the thiol functional chlorinated carbon clusters microspheres,and the as-obtained Pd/microspheres also possess high catalytic activity and stability for the reduction of 4-nitrophenol.The research on the catalytic activity and stability of Au/microspheres and Pd/microspheres reveals that the chlorinated carbon clusters microspheres are useful in the noble metal catalysis applications.(3) Based on the strong complexation between heavy metal ion and thiol groups, the thiol functional chlorinated carbon clusters microspheres is a potential heavy metal ion adsorbent.By using the chlorinated carbon clusters microspheres which obtained by the solvothermal Williamson reaction between the C₁₆Cl₁₀ and disodium salt of 2,5-dimercapto-1,3,4-thiadizaole as the adsorbent for single heavy metal ion (i.e.Pb²⁺,Hg²⁺,and Cd²⁺),the chlorinated carbon clusters microspheres shows high adsorption capacity for the Pb²⁺,about 120 mg/g.Furthermore,the result of using the chlorinated carbon clusters microspheres as the adsorbent for the mixture of Pb²⁺, Hg²⁺,and Cd²⁺ reveals that the carbon clusters microspheres possess high selective adsorption for Pb²⁺.Study on the optimum conditions for Pb²⁺ adsorption by the microspheres reveals that chlorinated carbon clusters microspheres possess superior adsorption capacity under the weak acidity condition(pH=5～7).The difference in Pb²⁺ adsorption capacity for the chlorinated carbon clusters microspheres composed of different components present their different content of thiol groups on the surface. Furthermore,the chlorinated carbon clusters microspheres possess superior adsorption capacity compared with the commercial inorganic sorbent,such as TiO₂ (P25),Al₂O₃,and Fe₂O₃.The research on the adsorption capacity and selective adsorption of the chlorinated carbon clusters microspheres for Pb²⁺ adsorption reveals that the chlorinated carbon clusters microspheres have potential application in lead industrial wastewater treatment.