Organometallic Functionalization of Colloidal Nanocrystal Surfaces for Catalysis

在化学系化学催化项目的支持下，圣母大学的Emily Tsui将研究利用光加速重要化学转化的新方法。具有半导体性质的纳米材料在光诱导化学转化方面的研究由来已久。然而，精确测量和控制这些材料的表面性质的化学反应性是很难实现的实验。该项目将专注于利用附着在光吸收纳米粒子上的金属中心来提供纳米粒子特性的信息，并作为重要催化转化的反应中心，如碳-碳键形成反应。从这些研究中获得的结果将指导新的光促进反应的发展。这项资助也将支持研究生和本科生在这个跨学科领域的研究训练。徐教授的研究团队将积极参与与本地小学生有关的外展活动，重点发展以纳米材料为基础的化学教育模块。此外，还将由研究生和徐博士制作有关电化学和催化实践主题的教育视频，并在网上免费提供给公众。在这些研究中，来自圣母大学的Emily Tsui和她的团队将研究将有机金属羰基片段与半导体纳米晶体量子点表面配合用于光催化反应。由于量子点具有可调的光吸收特性，因此它们已成为许多反应的光敏剂和光催化剂，但关于表面化学对这些转化的影响仍然存在许多问题。Tsui团队将探索使用表面结合的金属羰基碎片作为量子点表面效应的光谱报告者，包括表面偶极矩，这可以与光催化相关的性质（如带边势）相关。这些光谱特征的定量模型的发展有望导致更详细地了解表面效应如何在光氧化还原转化过程中促进量子点的反应性。此外，徐博士将研究在光催化转化过程中使用表面结合的有机金属碎片作为催化中心。研究生将接受有机金属化学和材料表征方法的培训，为他们提供跨学科的专业经验。这些学生还将通过参加外联活动和编写将在网上传播的一系列电化学视频，接受科学传播方面的培训。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 the support of the Chemical Catalysis program in the Division of Chemistry, Emily Tsui of the University of Notre Dame will study new ways of using light to accelerate important chemical transformations. Nanomaterials with semiconductor properties have long been studied for light-induced chemical transformations. However, the precise measurement and control of the surface properties of these materials for chemical reactivity are difficult to achieve experimentally. The project will focus on using metal centers attached to light-absorbing nanoparticles to provide information about the properties of the nanoparticles, and to act as reaction centers for important catalytic transformations such as carbon-carbon bond formation reactions. The results obtained from these studies will guide the development of new light-promoted reactions. This grant will also support the research training of graduate and undergraduate students in this interdisciplinary field. Professor Tsui’s research team will actively participate in outreach activities involving local elementary school students, with a focus on developing educational modules on nanomaterials-based chemistry. Educational videos on practical topics in electrochemistry and catalysis will also be produced by the graduate students and Dr. Tsui, and will made freely available online to the general public.In these studies Emily Tsui and her team at the University of Notre Dame will study the use of organometallic metal carbonyl fragments coordinated to the surfaces of semiconductor nanocrystal quantum dots for photocatalytic reactions. Quantum dots have been targeted as photosensitizers and photocatalysts for many reactions due to their tunable light-absorbing properties, but many questions remain regarding the effects of surface chemistry upon these transformations. The Tsui group will explore the use of surface-bound metal carbonyl fragments to act as spectroscopic reporters of quantum dot surface effects including the surface dipole moment, which can correlate to photocatalytically-relevant properties such as band edge potentials. The development of a quantitative model of these spectroscopic features is expected to lead to a more detailed understanding of how surface effects contribute to quantum dot reactivity during photoredox transformations. Additionally, Dr. Tsui will study the use of the surface-bound organometallic fragments to act as catalytic centers during photocatalytic transformations. Graduate students will be trained in both organometallic chemistry and materials characterization methods, providing them interdisciplinary experience that will be professionally valuable. These students will also be trained in scientific communication through participation in outreach activities and in the preparation of a series of electrochemistry videos that will be disseminated online.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.