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

本研究课题由科学研究资助计划（B）（2）资助，旨在通过引入具有氧化还原活性或与离子相互作用的化学物种，开发新型的有机电子和离子导电材料。金属离子和有机硫部分。在本研究中得到的这些导电聚合物显示出在导电聚合物主链和引入的电活性物种之间的容易的电子转移。以N-异丙基丙烯酰胺（NIPA）为基质，制备了温度响应性相转变凝胶，用于控制钌配合物的氧化还原反应和半导体催化剂的催化活性。 ...更多信息 n对过氧化氢（H_2O_2）电还原的影响。NIPA凝胶中氯化血红素的表观活性可能是通过改变温度来控制的，从而诱导NIPA凝胶在溶胀（低温）和收缩（高温）状态之间的相变。通过<-3>对交联度、交联长度和交联结构的精细控制，成功地制备了离子电导率大于10^ 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基团（-CH_2-CH_2-O-），得到了能够抑制锂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质是非常有前途的。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