Control of Electron-transfer Processes for Functionalization of Redox Active Thin Films

这项获科学研究资助基金(B)(2)资助的研究课题，是发展新型有机电子及离子导电材料，透过引入各种具有氧化还原活性或与离子相互作用的化学物质，使其分子功能化。通过引入二茂铁、金属离子和有机硫基团等电活性物质，合成了聚苯胺和聚吡咯等电活性导电聚合物的衍生物。本研究获得的导电聚合物在导电聚合物主链和引入的电活性物质之间表现出容易的电子转移。此外，铜离子磺化聚苯胺对2,5-二巯基-1,3,4-噻二唑等有机含硫化合物的氧化还原反应表现出更强的电催化活性。制备了基于n -异丙基丙烯酰胺（NIPA）的热响应型相变凝胶，用于控制钌配合物的氧化还原反应和半甲基丙烯酰胺对过氧化氢（H_2O_2）电还原的催化活性。可能通过改变温度来控制并入NIPA凝胶中的hemin的表观活性，从而诱导NIPA凝胶在肿胀（低温）和收缩（高温）状态之间的相变。开发高离子电导率的锂电池凝胶电解质是本研究的另一个课题。通过精心控制交联度、长度和结构，成功制备了离子电导率大于10^<-3>S/cm的丙烯腈凝胶电解质。此外，通过在甲基丙烯酸甲酯基聚合物基体中引入环氧乙烷（- ch_2 - ch_2 - o -），得到了能够抑制金属锂电极与凝胶电解质界面上锂枝晶形成的凝胶电解质。这些凝胶电解质作为超高能量密度聚合物锂电池的电解质具有很高的应用前景。少

The subject of this research supported by Grant-in-Aid for Scientific Research (B)(2) is to develop novel organic electron-and ion-conducting materials which are molecularly functionalized by introducing various chemical species which are redox active or interactive with ions.Derivatives of electroacitve, conducting polymers such as polyaniline and polypyrrole were synthesized by introducing electroacitve species such as ferrocene, metal ions and organosulfur moieties. These conducting polymers obtained in this research showed facile electron transfers between the conducting polymer main chains and introduced electroactive species. Furthermore, sulfonated polyaniline with copper ions showed enhanced electrocatalytic activity toward redox reactions of organosulfur compounds such as 2,5-dimercapto-1,3,4-thiadiazole.Thermoresponsive phase transition gels based on N-isopropylacrylamide (NIPA) were prepared for control of redox reactions of a ruthenium complex and catalytic activity of hemi … More n toward the electroreduction of hydrogen peroxide (H_2O_2). It was possible that apparent activity of hemin incorporated into the NIPA gels was controlled by changing temperature to induce the phase transition of the NIPA gels between swollen (at a low temperature) and shrunken (at a high temperature) states.Development of gel electrolytes with high ionic conductivity for lithium rechargeable batteries is another subject of this research. Acrylonitrile gel electrolytes with ion conductivity of more than 10^<-3>S/cm were successfully obtained by elaborately controlling the degree, length and structure of cross-links. Furthermore, by introducing ethylene oxide moiety (-CH_2-CH_2-O-) into methyl methacrylate-based polymer matrix, gel electrolytes which are capable of repressing formation of lithium dendrites at the interface between the gel electrolytes and metallic lithium electrode were obtained. These gel electrolytes are highly promising as an electrolyte for polymer lithium batteries with ultra high energy density. Less