CAS: Collaborative Research: Design, Characterization, and Modeling of Metal Nanocluster Electrocatalysts Linked to Three-Dimensional Graphene

在化学系化学结构、动力学和机理b项目的支持下，马萨诸塞大学洛厄尔分校化学系的周国藩、Jerome Delhommelle和闫明迪以及新罕布什尔大学化学系的李功虎正在开发用于电催化应用的新型石墨烯纳米复合材料。本研究的目标是开发一种利用金属纳米团簇（MNCs）和原始石墨烯构建电催化剂的新策略，用于电化学CO2还原。通过提出的研究获得的知识有望提高我们对固体-固体界面如何影响纳米复合材料电催化性能的基本理解。这样的理解可以指导可再生能源应用的创新设备的设计和制造。该项目将为本科生和研究生研究人员提供良好的培训机会，促进妇女和代表性不足的少数民族参与STEM（科学、技术、工程和数学）研究。该项目还包括为K-12学生设计的外展活动（多个为期一天的研讨会），以增加纳米科学，化学和材料科学学科的国家人才管道。石墨烯负载的纳米复合材料由于其在催化等各个领域的潜在应用而引起了越来越多的研究人员的兴趣。然而，在石墨烯基纳米复合催化剂中，催化剂与石墨烯之间的固体-固体界面通常定义不清。理解和优化这样的界面对于二氧化碳还原等电催化应用尤为重要，其中电子需要从石墨烯电极迁移到催化剂上。石墨烯的分子功能化为制备具有增强电子转移动力学的新型电催化剂（特别是MNCs）提供了巨大的机会。本项目以金纳米团簇（aunc）为模型MNCs，旨在开发一种利用MNCs和原始石墨烯构建创新电催化剂的新策略。具体来说，aunc将通过一系列合理设计的分子连接剂共价附着在三维原始石墨烯（3DG）电极上。这个项目需要四个研究小组的专业知识互补。将采用合成、计算建模、电化学和光谱学相结合的方法来研究连接体结构如何影响AuNC-3DG电催化CO2还原性能。预计所得结果将增强我们对在分子水平上控制固-固界面如何影响电化学器件中纳米复合材料性能的基本理解。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 of the Chemical Structure, Dynamics & Mechanisms-B Program of the Division of Chemistry, Kwok-Fan Chow, Jerome Delhommelle, and Mingdi Yan of the Department of Chemistry at the University of Massachusetts Lowell and Gonghu Li of the Department of Chemistry at the University of New Hampshire are developing new classes of graphene-supported nanocomposite materials for electrocatalytic applications. The goal of this research is to develop a new strategy for constructing electrocatalysts from metal nanoclusters (MNCs) and pristine graphene for electrochemical CO2 reduction. Knowledge gained through the proposed research is expected to improve our fundamental understanding of how the solid-solid interface impacts the electrocatalytic properties of nanocomposites. Such understanding could guide the design and fabrication of innovative devices for renewable energy applications. This project will provide excellent training opportunities for undergraduate and graduate researchers, promoting the participation of women and underrepresented minorities in STEM (science, technology, engineering and mathematics) research. This project also includes outreach activities (multiple one-day workshops at both institutions) designed for K-12 students to increase the national talent pipeline in nanoscience, chemistry, and materials science disciplines.Graphene-supported nanocomposite materials have attracted increasing interest among researchers due to their potential applications in various areas including catalysis. However, in graphene-based nanocomposite catalysts, the solid-solid interfaces between catalysts and graphene are often poorly defined. Understanding and optimizing such interfaces is particularly important for electrocatalytic applications such as CO2 reduction, in which electrons need to migrate from the graphene electrode to the catalyst. Molecular functionalization of graphene offers enormous opportunities to prepare new electrocatalysts (particularly MNCs) with enhanced electron transfer kinetics. Using gold nanoclusters (AuNCs) as the model MNCs, this project aims to develop a new strategy for constructing innovative electrocatalysts from MNCs and pristine graphene. Specifically, AuNCs will be covalently attached onto three-dimensional pristine graphene (3DG) electrodes through a series of rationally designed molecular linkers. This project requires complementary expertise from four research groups. A combination of synthesis, computational modeling, electrochemistry, and spectroscopy will be employed to investigate how the linker structure affects the performance of the AuNC-3DG electrocatalytic CO2 reduction. It is anticipated that the results obtained will enhance our fundamental understanding of how control over solid-solid interfaces at the molecular level impacts the performance of nanocomposite materials in electrochemical devices.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.