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1-氯-2-甲酰基乙烯基二茂铁与钌乙烯基吡啶配合物的电化学共聚

Electrocopolymerization of (1-Chloro-2-formylvinyl)ferrocene and Vinylpyridine Complex of Ruthenium

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【作者】 刘晓霞黄永德孙克张宝砚张玲

【Author】 LIU, Xiao Xia , a WONG, Wing Tak b SUN, Ke a ZHANG, Bao Yan a ZHANG, Ling a ( a Department of Chemistry, Northeastern University, Shenyang 110004) ( b Department of Chemistry, The University of Hong

【机构】 东北大学化学系香港大学化学系东北大学化学系 沈阳110004香港沈阳110004沈阳110004

【摘要】 利用与钌乙烯基吡啶配合物 [Ru(bpy) (vpy) 2 ](PF6 ) 2 (1) (bpy =2 ,2′ bipyridine ,vpy =4 vinylpyridine)的电化学共聚 ,加速了 1 氯 2 甲酰基乙烯基二茂铁 (CFVF) (2 )的电化学聚合速度 ,制备了具有Fc+ Fc和Ru3+ Ru2 + 电化学响应的 1~ 2共聚膜 .探讨了共聚膜对酚类电化学氧化的催化活性和邻二硝基苯 (ONB)在膜上的氧化还原反应 .

【Abstract】 Chloro 2 formylvinyl)ferrocene (2) and [Ru(bpy)(vpy) 2](PF 6) 2 (1) (bpy=2,2′ bipyridine, vpy=4 vinylpyridine) were copolymerized through reductive electropolymerization in acetonitrile containing 0 1 mol·L -1 TBAH as supporting electrolyte The electropolymerization was conducted by cyclic voltammetry from 0 7 to -2 15 V vs. Ag +/Ag, using glassy carbon as the working electrode and platinum wire as counter electrode. After thoroughly rinsed by acetone and acetonitrile, the resulting film demonstrated two pairs of redox peak when cyclic voltammetry scanned in the monomer free electrolyte solution, corresponding to Fc +/Fc (0 16 V vs. Ag +/Ag) and Ru 3+ /Ru 2+ (0 93 V vs. Ag +/Ag) couples respectively. Surface coverage of electroactive sites, based on Fc +/Fc couple, was 1×10 -8 mol·cm -2 , the same as the single polymer of 2 made through more than 79 times scan. The polymerization of 2 was enhanced by copolymerization with 1 since the copolymer with a 1×10 -8 mol·cm -2 surface coverage of electroactive ferrocene sites was made by only 10 times scan. This is also proved by the much stronger redox peak currents of Fc +/Fc couple in copolymer compared with those in homopolymer of 2 made under the similar conditions. Electrooxidations of 4 methoxylphenol and catechol in aqueous NaOAc solution catalyzed by the copolymer demonstrated much stronger oxidation current of the phenol at this electrode compared with those at GC. Cyclic votammetry of o nitrobenzene at electrode coated with the copolymer was very different from that at GC. The reoxidation of reduced o nitrobenzene shifted positively to the potential of Fc +/Fc couple, indicating that the reoxidation was mediated by the oxidation of electroactive ferrocene sites in the polymer.

【关键词】 电化学聚合二茂铁
【Key words】 electropolymerizationferroceneruthenium
【基金】 教育部留学回国人员科研启动基金;沈阳市科委基金 (No .2 0 0 12 2 8 0 7 15 )资助项目
  • 【文献出处】 化学学报 ,Acta Chimica Sinica , 编辑部邮箱 ,2002年08期
  • 【分类号】O631.5
  • 【被引频次】18
  • 【下载频次】178
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