CAREER:Hierarchical Modeling for Rational Catalyst Design in Aqueous Conditions

摘要（Getman，1554385）拟议的研究将完善分子模拟模型的催化反应中存在的液态水和应用计算的电化学过程氨合成，可能取代长期存在的，但能源密集型，哈伯-博世气相过程。 该研究与一项教育计划相结合，该计划向从高中到研究生研究的各个层次的学生介绍分子水平的模拟概念。近年来，由于计算机资源的快速改善，对催化材料和过程的理论理解已经取得了显着进展。这种理论上的理解正在简化催化剂发现的过程，并将催化领域转向新工艺和材料的预测，远离传统的试错方法。 然而，这种转变在液相催化领域，特别是电催化领域一直很慢，这在很大程度上是因为对流体分子和催化剂表面之间发生的相互作用的不完全理解。 这里提出的研究将通过考虑它们的自由能来更好地理解这些相互作用，而以前的治疗只考虑它们的自由能。 传统的建模方程将被细化和扩展，添加，第一次，自由能的贡献，由于旋转，平移，和液相分子和物种之间发生的相互作用吸附到催化剂表面。 然后，改进的模型将被引导到了解液态水和气态氮之间的反应在电催化环境下产生氨在接近环境温度和压力条件下。 改进后的模拟模型将为更合理的方法在广泛的液相催化反应中发现催化剂铺平道路，教育材料将在分子水平的现象和有效使用分子模拟工具方面培训未来几代学生。

Abstract (Getman, 1554385)The proposed research will refine molecular simulation models for catalytic reactions in the presence of liquid water and apply the calculations to an electrochemical process for ammonia synthesis that could potentially replace the long-standing, but energy intensive, Haber-Bosch gas phase process. The research is integrated with an educational plan that introduces molecular level simulation concepts to students across levels ranging from high school to graduate research.Theoretical understanding of catalytic materials and processes has advanced significantly in recent years due to rapid improvements in computer resources. This theoretical understanding is streamlining the process of catalyst discovery and moving the field of catalysis toward the prediction of new processes and materials and away from the traditional trial-and-error approach. However, this transition has been slow in the area of liquid phase catalysis, especially electrocatalysis, in large part because of incomplete understanding of the interactions that occur between fluid molecules and the catalyst surface. The research proposed here will take a large step toward better understanding these interactions by considering their free energies, whereas prior treatments have only considered their enthalpies. Traditional modeling equations will be refined and extended by adding, for the first time, free energy contributions due to rotation, translation, and interaction occurring between liquid-phase molecules and species adsorbed to the catalyst surface. The refined models will then be directed toward understanding the reaction between liquid water and gaseous nitrogen in an electrocatalytic environment to produce ammonia under near-ambient temperature and pressure conditions. The improved simulation models will pave the way for a more rational approach to catalyst discovery across a broad range of liquid phase catalytic reactions, and the educational materials will train coming generations of students in molecular-level phenomena and the effective use of molecular simulation tools.