DMREF: Collaborative Research: Integration of Computation and Experiments to Design a Versatile Platform for Crystal Engineering

1629398/1628960 Palmer，Jeremy/Rioux，Robert M.该项目致力于改进晶体沸石材料的设计，这些材料用于从催化和储能到电子设计等各种应用。沸石材料的纳米孔径非常适合于化工和石油工业中的广泛分离和选择性催化转化。改善沸石性能的一个很有前途的策略是使用有针对性的合成方法来调整晶体的形状和大小。该项目的总体目标是开发计算机模拟方法，用于快速识别小分子化合物，即可用于控制沸石晶体形状和大小的生长改进剂。这将加快开发新的催化剂、吸附剂和分离材料，将廉价和丰富的天然气资源转化为燃料和高价值化合物，同时减少有毒排放。在天然和合成结晶中广泛使用的一种控制结晶习性和形态的技术是使用修饰剂，修饰剂是分子(或大分子)添加剂，具有选择性地吸附在特定晶面上并改变各向异性生长速度(S)的亲和力。在这一研究领域中，最关键的挑战是，无论材料和应用如何，对控制改性剂对不同晶体表面的吸附和结合专一性的分子水平相互作用和热力学驱动力的了解还不完全。本项目的重点是集成沸石的合成、表征和建模，开发一个经过实验验证的计算平台，用于基于平衡吸附性质表征生长改进剂对结晶的影响。这将通过解决三个具体目标来实现：(1)利用实验基准数据开发、验证和迭代改进用于预测改性剂吸附的密度泛函理论和分子模拟模型；(2)评估模型的预测性和对其他改性剂-沸石系统的可转移性；以及(3)阐明结构-性质关系作为建立改性剂选择指南的手段。这一计算平台将提高我们对调控修饰剂有效性和特异性的机制的理解，从而为识别有效的修饰剂提供基础，并有可能将其发现速度加快两个数量级。从该项目获得的基本知识将作为合理设计生长改进剂的翻译指南，促进改进的结晶过程控制策略的开发，这些应用涉及从催化到分离和吸附等各种应用。该项目还将为K-12学生和本科生提供教育和推广部分，包括为休斯顿地区的高中生提供建立分子沸石模型的机会。

1629398/1628960Palmer, Jeremy/Rioux, Robert M.The project addresses improved designs of crystalline zeolite materials used in applications ranging from catalysis and energy storage to electronics design. The nanometer sized pores of the zeolite materials are ideally suited for a wide range of separations and selective catalytic conversions in the chemical and petroleum industries. A promising strategy for improving the properties of zeolites is to tune crystal shape and size using targeted synthetic approaches. The overall goal of this project is to develop computer simulation methods for rapidly identifying small-molecule compounds known as growth modifiers that can be used to control zeolite crystal shape and size. This will accelerate the development of new catalysts, adsorbents, and separations materials for converting inexpensive and abundant sources of natural gas into fuels and high-valued compounds while simultaneously lowering toxic emissions. A technique that is broadly utilized in both natural and synthetic crystallization to control crystal habit and morphology is the use of modifiers, which are molecular (or macromolecular) additives that possess an affinity for selectively adsorbing on specific crystal faces and altering the anisotropic rate(s) of growth. The most critical challenge in this field of research, irrespective of the material and application, is the incomplete understanding of the molecular-level interactions and thermodynamic driving forces that govern the adsorption and binding specificity of modifiers to different crystal surfaces. The focus of this project is to integrate zeolite synthesis, characterization, and modeling to develop an experimentally-validated computational platform for characterizing growth modifier effects on crystallization based on equilibrium adsorption properties. This will be achieved by addressing three specific aims: (1) develop, validate, and iteratively refine density functional theory and molecular simulation models for predicting modifier adsorption using experimental benchmark data; (2) assess model predictability and transferability to other modifier-zeolite systems; and (3) elucidate structure-property relationships as a means of establishing guidelines for modifier selection. This computational platform will improve our understanding of the mechanisms governing modifier efficacy and specificity, thereby providing a foundation for identifying effective modifiers and potentially accelerating their discovery by two orders of magnitude. The fundamental knowledge gained from this project will serve as a translational guide for the rational design of growth modifiers, fostering the development of improved strategies for controlling crystallization processes relevant to applications ranging from catalysis to separations and adsorption. The project will also provide educational and outreach components to K-12 students and undergraduates, including opportunities for Houston-area high school students to build molecular zeolite models.