SYNTHESIS, ASSEMBLY, AND ELECTROCHROMIC BEHAVIOR OF NANOSTRUCTURED CONJUGATED POLYMER/METAL INTERFACES

在这个项目中，乔治亚理工学院的Vladimir Tsukruk教授和John Reynolds教授在美国国家科学基金会的大分子、超分子和纳米化学（MSN）项目的支持下，制造了由聚合物结合金和银纳米级颗粒组成的新材料。目前，可以设计出由塑料或聚合物制成的新型变色材料，其颜色可以从紫色调到红色，透明度可以从绝对透明到完全不透明。由这些聚合物制成的柔性滤光片可以阻挡或偏转有害的短波（如导致晒伤的波长），并传输对阳光照射加热有用的长波。目前已知的大多数滤波器都是固定用于特定功能的，在制造后不能更改。利用光、化学环境或施加的小电场，可以改变这些滤光片的颜色和透明度。这些新结构的潜在用途是促进黄昏或黎明柔性太阳能电池的智能光采集，并创造可穿戴电子设备，允许持续监测佩戴者的健康状况。此外，这项工作还对化学教育和教学产生了影响，通过开发精选的内部教程来定义共轭聚合物合成和电化学的基本方面，这些都是熟悉这些技术所必需的。这个项目的一个更广泛的影响是加强对研究生和本科生的培训，重点是他们尽早参与跨学科的基础研究，并积极招募代表性不足的群体。为了扩大这些努力的范围，开发了网络研讨会教程，并通过一个使用WIKI软件的网站向一般科学界发布。这项工作影响能源科学、聚合物和材料化学、电化学和有机电子学。这项跨学科研究的优点是对电化学驱动的大分子转化的行为和驱动分子机制的基本理解的发展。这些转化影响了无机界面附近大分子的超分子组织、氧化还原状态以及电子和离子电导率的平衡。利用一系列新合成的沉积在金属界面上的聚合物，研究了与电致变色行为相关的各种过程。这项工作包括合成具有带隙、颜色和氧化电位变化的新型水溶性和可加工共轭聚电解质。围绕贵金属纳米结构的界面聚合物层的组装平衡了局部和全局聚合物链构象、电荷和氧化还原电位分布。这些因素对于控制聚合物的光学性质至关重要，包括吸光度、折射率和电化学氧化过程中的等离子体相互作用。该项目的更广泛影响包括学生参与跨学科的基础研究，并通过辅导网络研讨会向更广泛的教育界传播新技能和知识。

In this project, Professors Vladimir Tsukruk and John Reynolds of Georgia Institute of Technology are supported by the Macromolecular, Supramolecular, and Nanochemistry (MSN) Program of the NSF to make new materials consisting of polymers combined with gold and silver nanometer-sized particles. Currently, novel color-changing materials made of plastic or polymers can be designed so that their colors can be tuned from purple to red and their transparency from absolutely clear to completely opaque. Flexible filters made from these polymers can block or deflect harmful short wavelengths (like those that cause sunburn) and transmit long wavelengths useful for sun-illuminated heating. Most of the filters known today are fixed for a particular function and cannot be changed after fabrication. It is possible to change the color and transparency of these filters using light, the chemical environment, or small applied electric fields. The potential uses of these novel structures are to facilitate intelligent light harvesting for flexible solar cells at dusk or dawn and to create wearable electronics that allow the continuous monitoring of the wearer's health. Further, this work has an impact in regard to chemistry education and teaching through the development of select in-house tutorials defining the fundamental aspects of conjugated polymer synthesis and electrochemistry that are required in order for one to be conversant in these technologies. A broader impact of this project is the enhanced training of graduate and undergraduate students with an emphasis on their early involvement in interdisciplinary, fundamental research with active recruitment of underrepresented groups. To broaden the scope of these efforts, webinar tutorials are developed and made available through a website that uses WIKI software for release to the general scientific community. This work impacts energy sciences, polymer and materials chemistry, electrochemistry, and organic electronics.The merit of this cross-disciplinary study is the development of a fundamental understanding of the behavior and driving molecular mechanisms of electrochemically-driven transformations of macromolecules. These transformations affect the supramolecular organization, redox state, and the balance of electronic and ionic conductivities of macromolecules in proximity to inorganic interfaces. The various processes associated with electrochromic behavior are investigated utilizing a series of newly synthesized polymers deposited on metal interfaces. The work includes synthesis of novel water-soluble and processable conjugated polyelectrolytes with variations in band gap, color, and oxidation potential. The assembly of interfacial polymer layers around noble metal nanostructures balances local and global polymer chain conformation, charge, and redox potential distribution. These factors are critical for controlling the optical properties of the polymers including absorbance, refractive index, and plasmonic interactions during electrochemical oxidation. The broader impacts of this project include the involvement of students into cross-disciplinary, fundamental research and the dissemination of new skills and knowledge to the broader educational community through tutorial webinars.