Molecular Interrogation of Coupled Electron- and Phase-Transfer Reactions

在化学系化学结构、动力学和机理 A (CSDM-A) 项目的支持下，犹他大学的 Rodrigo Noriega 以及犹他大学的 Henry White 和芝加哥大学的 Gregory Voth 将研究耦合电子和相转移过程。这些反应中，电子转移与离子或中性分子跨相界的传输一起发生，存在于各种工业过程和储能技术中。由于缺乏对这些多步骤过程中关键步骤的中间体的分子尺度理解，理解这些反应具有挑战性。诺列加博士和他的团队将把明确分子系统上的超快光谱学和电化学实验与计算方法结合起来，独立研究耦合电子和相转移反应。对这些反应的深入了解有可能影响能量储存和稀有金属离子分离。除了对学生进行研究培训外，该团队还将组织一个年度研讨会，其中包括实验室演示和专业发展机会。复杂界面处的探测反应，即氧化还原活性分析物通过电极进行电子转移，同时由于其氧化态溶解度不同而在两个不混溶相之间进行转移，将通过三相界面伏安法、超快瞬态吸收光谱和多尺度电化学分子动力学模拟来研究。为了告知和测试捕获分子尺度动力学和宏观结果的新模型，将采用一个分层框架，该框架将计算与跨越时间和长度的数量级的光谱和电化学观察相结合。溶剂化壳层交换的能量学和动力学，包括界面波动的作用，将通过关联相特定的电化学响应、受控静电条件下相边界的时间分辨吸收和发射测量以及多尺度分子动力学模拟来确定。独立监测明确界面上的离子和电子转移电流，同时系统地改变其双电层结构，再加上高效的恒电位电化学模拟，将确定三相界面上相关耦合电子和相转移反应的分子结构的作用。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力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, Rodrigo Noriega of the University of Utah along with Henry White from the University of Utah and Gregory Voth from the University of Chicago will study coupled electron and phase transfer processes. These reactions, where electron transfer occurs alongside the transport of ions or neutral molecules across a phase boundary, are present in a wide variety of industrial processes and energy storage technologies. Understanding these reactions is challenging due to the lack of molecular-scale understanding of intermediates at critical steps in these multistep processes. Dr. Noriega and his team will integrate ultrafast spectroscopy and electrochemistry experiments on well-defined molecular systems with computational methods to study coupled electron and phase transfer reactions independently. The resulting insight into these reactions has the potential to impact energy storage and rare metal ion separations. In addition to training students in research, the team will organize an annual workshop that includes lab demonstrations and professional development opportunities.Probe reactions at complex interfaces, whereby redox-active analytes undergo electron transfer with an electrode while also transferring between two immiscible phases due to the differential solubility of their oxidation states, will be studied with voltammetry at three-phase interfaces, as well as by ultrafast transient absorption spectroscopy, and multiscale electrochemical molecular dynamics simulations. To inform and test new models that capture molecular-scale dynamics and macroscopic outcomes, a hierarchical framework that combines computation with spectroscopic and electrochemical observation spanning orders of magnitude in time and length will be employed. The energetics and dynamics of solvation shell exchange, including the role of fluctuations at the interface, will be determined by correlating phase-specific electrochemical responses, time-resolved absorption and emission measurements at phase boundaries under controlled electrostatic conditions, and multiscale molecular dynamics simulations. Independently monitoring the ion- and electron-transfer currents at well-defined interfaces while systematically altering their electric double layer structure, along with efficient constant-potential electrochemical simulation, will identify the role of molecular structure of relevant coupled electron and phase transfer reactions at three-phase interfaces.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.