CAS-Climate: Basicity in the Excited State and under Interfacial Confinement: Fundamentals and Applications to Catalysis

在化学系化学结构、动力学和机理a （CSDM-A）项目的支持下，南加州大学的Jahan Dawlaty将研究电极表面附近的质子转移反应。质子在分子间的转移在许多产生高价值化学品的电化学反应中起着核心作用。然而，由于这些质子转移反应发生在万亿分之一秒内，并且发生在距离电极表面比一张纸薄1000倍的层上，因此研究它们是困难的。Dawlaty博士和他的学生将使用先进的激光光谱技术来触发电极表面附近小分子中的质子转移，并研究发生的化学反应。他们的发现可能有助于推进二氧化碳封存策略，以及影响太阳能转换和储存技术。此外，该项目将为研究生和本科生提供跨学科的研究机会，并与鲍登学院建立学生交换计划，以弥合教学和研究之间的差距。根据该合同，Dawlaty研究团队将研究电化学表面附近激发态酸碱反应的能量学和动力学，使用静态和时间分辨吸收和发射方法的组合，以及界面特定的振动光谱。第一个目标将集中在可以被光触发的小分子上，这些小分子可以吸收质子，并利用它们来驱动光催化循环。该项目将探索光碱度或光激发后pKa增加的分子原理，并努力建立一系列共轭杂环分子激发态碱度的设计规则。第二个目标是创造出令人沮丧的刘易斯酸碱对，并探索它们作为激活二氧化碳等小分子的高反应性口袋的潜力。该项目旨在利用这些现象来发现光催化和电化学中的新反应性，并将激发态质子转移的经验教训应用于与能量转换和存储相关的反应。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 Chemical Structure, Dynamics, and Mechanisms-A (CSDM-A) program in the Division of Chemistry, Jahan Dawlaty of University of Southern California will study proton transfer reactions near the surfaces of electrodes. The transfer of protons between molecules plays a central role in many of the electrochemical reactions that produce high-value chemicals. However, because these proton transfer reactions happen in trillionth of a second and occur in a layer that is one thousand times thinner than a sheet of paper from the electrode surface, studying them is difficult. Dr. Dawlaty and his students will use advanced laser spectroscopies to trigger proton transfer in small molecules near the electrode surface and study the chemical reactions that take place. Their discoveries could help advance CO2 sequestration strategies, as well as impact solar energy conversion and storage technologies. In addition, the project will provide interdisciplinary research opportunities for graduate and undergraduates students and establish a student exchange program with Bowdoin College for bridging the gap between teaching and research. Under this award, the Dawlaty research team will study the energetics and kinetics of excited state acid-base reactions near electrochemical surfaces using a combination of static and time-resolved absorption and emission methods, as well as interface-specific vibrational spectroscopies. The first aim will focus on small molecules that can be triggered by light to take up protons and use them to drive photocatalytic cycles. The project will explore the molecular principles behind photobasicity, or increased pKa upon photoexcitation, and endeavor to establish design rules for excited state basicity in a range of conjugated heterocyclic molecules and beyond. The second aim will create frustrated Lewis acid-base pairs and explore their potential as pockets of high reactivity for activation of small molecules such as carbon dioxide. The project aims to exploit these phenomena to discover new reactivity in photocatalysis and electrochemistry and apply the lessons learned on excited state proton transfer to reactions that are relevant to energy conversion and storage.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.