Magnetic Effects on Electron Transfer Reactions

在这项由分析和表面科学化学计划支持的研究中，研究了磁效应对电子转移过程的影响并建立了模型。电子转移过程和磁场是普遍存在的，并通过电子自旋耦合，但磁场在电子转移中的作用知之甚少。从我们之前的工作来看，电极的磁修饰大大增强了学术上有趣的氧化还原探针和技术上重要的电源（包括燃料电池和电池）的电流。在这个项目中，磁增强反应动力学模型将通过在现有的电子转移模型上施加磁场和自旋项来发展。这些模型将根据现有数据和根据建模结果新收集的数据进行测试。这些模型将推动理论和实验科学的发展。从我们之前的工作中可以明显看出，通过磁修饰促进电子转移速率的一些更广泛的影响：具有更高功率密度和一氧化碳耐受性的燃料电池，具有一氧化碳耐受性的铂催化剂，以及具有更高可获得能量密度的碱性电池。所有这些都是潜在的变革性技术。理解磁场促进这些过程的原因将促进对电子转移反应的理解，并显著提高其他技术的开发效率。该项目是高度多学科的，整合了不同的化学领域，这是一个研究矩阵，可以培养出更好的学生。

In this research supported by the Analytical and Surface Science Chemistry Program, magnetic effects on electron transfer processes are investigated and modeled. Electron transfer processes and magnetic fields are ubiquitous and coupled through the electron spin, but the role of magnetic fields in electron transfer is poorly understood. From our prior work, magnetic modification of electrodes substantially enhances currents for academically interesting redox probes and for technologically important power sources including fuel cells and batteries. In this project, models for magnetically enhanced reaction kinetics will be developed by imposing magnetic field and spin terms on extant models of electron transfer. The models will be tested against existing data and data newly collected in light of the modeling results. The models will advance theoretical and experimental science.Some broader impacts of facilitating electron transfer rates by magnetic modification are apparent from our prior work: fuel cells with higher power density and carbon monoxide tolerance, platinum catalysts tolerant to carbon monoxide, and alkaline batteries with higher accessible energy density that are also made rechargeable. All are potentially transformative technologies. Appreciation of why magnetic fields facilitate these processes will advance the understanding of electron transfer reactions as well as lead to markedly more efficient development of other technologies. The project is highly multidisciplinary and integrates distinct fields of chemistry, a research matrix that leads to better trained students.