Quantifying the Effects of Disorder and Lateral Interactions on Chemically Modified Carbon Electrodes: Molecular Insights to Rationally Design Electrochemical Performance

在化学系大分子、超分子和纳米化学（MSN）项目的支持下，北卡罗来纳大学教堂山分校的Matthew R. Lockett和他的学生们正在研究无序和横向化学相互作用对化学修饰碳电极性能的影响。碳基电极被广泛使用，因为它们坚固耐用，而且它们的化学、电子和光学性质很容易通过官能团附着在它们的表面来调节。通过附加具有横向相互作用倾向的官能团对碳电极进行修饰，并对产物的物理化学性质进行表征。从该项目中获得的分子洞察力有望为重要应用（如传感、催化、电子和化学分离）的电化学系统的合理设计提供信息。将为研究生和本科生提供先进的综合和测量技术培训，并计划开展一些社区外展活动，重点是促进多样性、公平和包容，特别强调促进LGBTQ+参与科学研究和整个社会。根据该合同，Lockett研究团队将使用化学气相沉积技术开发具有可控成分的新型碳基电极材料。电极表面将被化学修饰成能与表面交换电子的官能团。新的仪器方法，包括扫描探针和单分子荧光显微镜，将开发表征修饰电极的表面结构和物理化学性质。将进行结构-功能导向的研究，具体确定表面分子无序如何影响模型配合物的电化学可逆性以及CO2还原催化剂的效率和选择性。通过进行实验获得的数据集将补充现有的通过横向相互作用量化无序的集成技术。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With support from the Macromolecular, Supramolecular, and Nanochemistry (MSN) Program of the Division of Chemistry, Matthew R. Lockett and his students at the University of North Carolina at Chapel Hill are investigating the effect of disorder and lateral chemical interactions on the properties of chemically modified carbon electrodes. Carbon-based electrodes are widely used because they are robust and their chemical, electronic and optical properties are readily tunable through the attachment of functional groups to their surfaces. Carbon electrodes will be modified by attaching functional groups with propensity for lateral interaction and the physicochemical properties of the products will be characterized. The molecular insight gained from conducting this project is expected to inform the rational design of electrochemical systems for important applications, such as sensing, catalysis, electronics, and chemical separations. A diverse group of graduate and undergraduate students will be trained in advanced synthesis and measurement techniques and several community outreach activities are planned with a focus on promoting diversity, equity, and inclusion with a special emphasis on promoting LGBTQ+ participation in scientific research and in society as a whole. Under this award, the Lockett research team will develop new carbon-based electrode materials with controlled composition using chemical vapor deposition techniques. Electrode surfaces will be chemically modified with functional groups that can readily exchange electrons with the surface. New instrumental methodologies, including scanning probe and single molecule fluorescence microscopies, will be developed to characterize the surface structure and physicochemical properties of the modified electrodes. Structure-function guided studies will be conducted to specifically determine how molecular disorder on the surface will affect the electrochemical reversibility of model complexes and the efficiency and selectivity of CO2 reduction catalysts. The datasets obtained from conducting the experiments will complement existing ensemble techniques that quantify disorder through lateral interactions.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.