CAREER:Hierarchical Modeling for Rational Catalyst Design in Aqueous Conditions

摘要（Getman, 1554385）提出的研究将完善液态水存在下催化反应的分子模拟模型，并将计算应用于氨合成的电化学过程，该过程可能取代长期存在但能源密集型的Haber-Bosch气相过程。这项研究与一个教育计划相结合，向从高中到研究生的学生介绍分子水平模拟的概念。近年来，由于计算机资源的快速发展，对催化材料和过程的理论认识有了显著的进步。这种理论理解简化了催化剂发现的过程，并将催化领域从传统的试错方法转向预测新工艺和新材料。然而，在液相催化领域，特别是电催化领域，这种转变一直很缓慢，这在很大程度上是因为对流体分子与催化剂表面之间发生的相互作用的理解不完全。这里提出的研究将在更好地理解这些相互作用方面迈出一大步，通过考虑它们的自由能，而之前的治疗只考虑它们的焓。传统的建模方程将被改进和扩展，首次加入由于旋转，平移和液相分子和吸附在催化剂表面的物质之间发生的相互作用而产生的自由能贡献。改进后的模型将用于理解在电催化环境中液态水和气态氮在接近环境温度和压力条件下产生氨的反应。改进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，教材将培养下一代学生在分子水平现象和有效使用分子模拟工具。

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.