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

本研究得到科学研究助学金(B)(2)的支持，旨在开发新型有机电子和离子导电材料，通过引入各种氧化还原活性或与离子相互作用的化学物种来实现分子功能化。通过引入二茂铁、金属离子和有机硫基团等电活性物种合成了电活性、导电聚合物聚苯胺和聚吡咯的衍生物。这些导电聚合物在导电聚合物主链和引入的电活性物种之间表现出很容易的电子转移。此外，铜离子的磺化聚苯胺对有机硫化合物的氧化还原反应具有增强的电催化活性，如基于N-异丙基丙烯酰胺的2，5-dimercapto-1，3，4-thiadiazole.Thermoresponsive相变凝胶的制备，以控制Ru络合物的氧化还原反应和半…的催化活性。对过氧化氢(H_2O_2)的电还原有较大的促进作用。可能通过改变温度来控制NiPA凝胶中氯化血红素的表观活性，从而诱导NIPA凝胶在膨胀(低温)和收缩(高温)状态之间的相变。开发用于锂二次电池的高离子导电性凝胶电解质是本研究的另一个主题。通过精心控制交联度、长度和结构，成功地制备了离子电导率大于10^&lt；-3&gt；S/cm的丙烯腈凝胶电解质。此外，将环氧乙烷(-CH_2-CH_2-O-)引入甲基丙烯酸甲酯基聚合物中，得到了能够抑制金属锂电极与凝胶电解质界面锂树枝晶形成的凝胶电解质。这些凝胶电解质作为具有超高能量密度的聚合物锂电池的电解液具有很好的应用前景。较少

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