Tuning the Thermodynamics and Kinetics of H+ and e- Transfer in Nanoconfined Environments

调整纳米环境中 H 和电子转移的热力学和动力学

• 批准号: 2204045
• 负责人: Mark Lipke
• 金额: $ 48.87万
• 依托单位: Rutgers University New Brunswick
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-01 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2204045&HistoricalAwards=false
• 关键词: Tuning; Thermodynamics; Kinetics; H+; Transfer

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Dr. Mark Lipke of Rutgers, The State University of New Jersey will design and study the chemical properties of hollow molecular cages. This project aims to provide detailed insights into how the acidity and electron-transfer properties of chemical species are altered when confined in nanometer-sized cavities. This fundamental knowledge is important for the development of chemical processes and catalytic materials for applications in advanced manufacturing. Alongside these efforts, the PI and his students will give talks at local high schools to illustrate how high school level chemical concepts are useful in cutting edge research. Dr. Lipke will also provide research internships for high school students and will develop new teaching materials for undergraduate courses.This research will be carried out using modular porphyrin nanocages that provide control over solvation and noncovalent interactions in nanoconfined environments to probe how these variables influence the thermodynamics and kinetics of H+ and e− transfer processes, including proton-coupled electron transfer (PCET) processes that are essential to many electrochemical transformations. This work has three aims. Aim I will develop robust, redox-active nanocages of different sizes, shapes, and H-bonding abilities that are well-suited to systematic chemical and electrochemical studies. Aim II will systematically measure how the pKa values and reduction potentials of encapsulated guests are affected by low relative permittivity nanocavities. Aim III will examine how the kinetics of H+ and e– transport to guest molecules bound in the nanocages can be controlled. The nanocages that will be employed in these studies can be characterized in both solution and the solid state, enabling detailed solution-phase mechanistic experiments to be performed on nanoporous structures that can be characterized with atomic resolution in the solid state. This research will make significant contributions to the mechanistic understanding of H+ and e− transfer processes in nanoconfined spaces, which in turn, will be useful for informing the rational design of porous structures with tunable properties for these important chemical processes.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.

在化学系高分子、超分子和纳米化学项目的支持下，新泽西州立大学罗格斯大学的Mark Lipke博士将设计和研究中空分子笼的化学性质。 该项目旨在详细了解化学物质的酸度和电子转移特性在纳米尺寸的空腔中被限制时如何改变。这些基础知识对于先进制造应用的化学工艺和催化材料的开发非常重要。 除了这些努力之外，首席研究员和他的学生还将在当地高中进行演讲，以说明高中水平的化学概念如何在前沿研究中发挥作用。 Lipke 博士还将为高中生提供研究实习机会，并为本科生课程开发新的教材。这项研究将使用模块化卟啉纳米笼进行，该纳米笼可控制纳米环境中的溶剂化和非共价相互作用，以探讨这些变量如何影响 H+ 和 e− 转移过程的热力学和动力学，包括质子耦合电子转移 (PCET) 过程 对于许多电化学转化至关重要。这项工作有三个目标。目标我将开发出不同尺寸、形状和氢键能力的坚固的氧化还原活性纳米笼，非常适合系统的化学和电化学研究。 Aim II 将系统地测量低相对介电常数纳米腔对封装客体的 pKa 值和还原电位的影响。目标 III 将研究如何控制 H+ 和 e- 传输到纳米笼中结合的客体分子的动力学。这些研究中使用的纳米笼可以在溶液和固态下进行表征，从而能够在纳米多孔结构上进行详细的溶液相机械实验，这些结构可以在固态下以原子分辨率进行表征。 这项研究将为纳米有限空间中 H+ 和 e− 传输过程的机械理解做出重大贡献，这反过来又有助于为这些重要化学过程的具有可调特性的多孔结构的合理设计提供信息。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。