Functional Carbon Nano-skins: Integrating Nanostructured Oxides with Molecular Systems

在这个由化学系的大分子，超分子和纳米化学项目资助的项目中，威斯康星大学麦迪逊分校的Robert Hamers教授和他的学生将把聚合物化学与表面化学结合起来，在金属氧化物纳米颗粒和分子系统（如分子光催化剂和捕光分子）之间形成超稳定的界面。 他们将探索在表面上创建的功能性“纳米皮肤”的合成和特性，使用金属氧化物如TiO 2作为模型系统。 为了形成坚固的层，带有多个反应基团的分子将被接枝到TiO 2表面;然后这些分子将被交联以形成二维表面网络，其中每个表面低聚物与表面有许多连接。然后将电化学活性物质连接到网络上，形成具有新的电化学和光电化学性质的功能层。基本性质，如电子转移速率将使用表面附着的二茂铁基团进行测量。将进行各种实验测量来表征层的化学和物理性质，以确定纳米厚分子层内的广泛横向交联是否可以导致具有新型电化学和光电化学性质的高度稳定的界面。该项目将为研究生，本科生和初级科学家提供表面化学技术和成为科学领导者所需的其他职业技能的最先进培训。学生将学习化学合成技术，表面表征，以及各种电化学和光电化学测量技术。他们还将接受口头和书面沟通，道德和领导力方面的培训。该研究将为表面分子层内和通过分子层的电荷转移过程提供重要的基础见解，并将有助于建立如何在无机材料和有机分子结构之间制造高度稳定界面的设计规则。无机-有机混合结构在一系列现有和新兴的商业技术中引起了极大的兴趣，并且在分子和金属氧化物（如TiO 2）之间形成水稳定界面的能力将在可再生能源等领域产生商业和社会影响。该项目还将通过提供与各种外部团体开展教育和外联活动的机会，对社会产生影响。

In this project, funded by the Macromolecular, Supramolecular, and Nanochemistry Program of the Chemistry Division, Prof. Robert Hamers of the University of Wisconsin-Madison and his students will integrate polymer chemistry with surface chemistry to make ultra-stable interfaces between metal oxide nanoparticles and molecular systems such as molecular photocatalysts and light-harvesting molecules. They will explore the synthesis and properties of functional "nano-skins" created on surfaces, using metal oxides such as TiO2 as model systems. In order to form robust layers, molecules bearing multiple reactive groups will be grafted to TiO2 surfaces; these will then be cross-linked to form two-dimensional surface nets in which each surface oligomer has many linkages to the surface. Electrochemically active species will then be linked to the net to form functional layers with novel electrochemical and photoelectrochemical properties. Fundamental properties such as electron transfer rates will be measured using surface-attached ferrocene groups. A variety of experimental measurements will be performed to characterize the chemical and physical properties of the layers in order to establish whether extensive lateral cross-linking within nanometer-thick molecular layers can lead to highly stable interfaces with novel electrochemical and photoelectrochemical properties. This project will provide graduate students, undergraduate students, and junior scientists with state-of-the-art training in the techniques of surface chemistry and other career skills necessary to become scientific leaders. Students will learn techniques of chemical synthesis, characterization of surfaces, and a variety of electrochemical and photoelectrochemical measurement techniques. They will also receive training in oral and written communication, ethics, and leadership. The research will provide important fundamental insights into charge-transfer processes within and through molecular layers at surfaces and will help to establish design rules for how to fabricate highly stable interfaces between inorganic materials and organic-based molecular structures. Inorganic-organic hybrid structures are of great interest in a range of existing and emerging commercial technologies, and the ability to make water-stable interfaces between molecules and metal oxides such as TiO2 would have both commercial and societal impact in areas such as renewable energy. The project will also impact society by providing opportunities for educational and outreach activities with a diversity of outside groups.