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

palmer, Jeremy/Rioux, Robert m .该项目解决了从催化和能量存储到电子设计等应用中使用的晶体沸石材料的改进设计。沸石材料的纳米孔径非常适合于化学和石油工业中广泛的分离和选择性催化转化。改善沸石性质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，用于快速识别被称为生长调节剂的小分子化合物，这些化合物可用于控制沸石晶体的形状和大小。这将加速开发新的催化剂、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，同时降低有毒物质的排放。在自然结晶和合成结晶中广泛使用的一种技术是使用改性剂来控制晶体习性和形态，改性剂是分子（或大分子）添加剂，具有选择性吸附在特定晶体表面和改变生长各向异性速率的亲和力。无论材料和应用如何，这一研究领域最关键的挑战是对分子水平的相互作用和控制改性剂在不同晶体表面的吸附和结合特异性的热力学驱动力的不完全理解。该项目的重点是整合沸石合成，表征和建模，以开发一个实验验证的计算平台，用于表征基于平衡吸附性质的生长调节剂对结晶的影响。这将通过解决三个具体目标来实现：(1)开发，验证和迭代完善密度泛函理论和分子模拟模型，用于使用实验基准数据预测改性剂吸附；(2)评估模型的可预测性和对其他改性剂-沸石体系的可转移性；(3)阐明结构-性质关系，作为建立修饰语选择准则的手段。这个计算平台将提高我们对修饰剂功效和特异性控制机制的理解，从而为识别有效的修饰剂提供基础，并有可能将它们的发现速度提高两个数量级。从该项目中获得的基本知识将作为合理设计生长调节剂的转化指南，促进开发与催化、分离和吸附等应用相关的控制结晶过程的改进策略。该项目还将为K-12学生和本科生提供教育和推广组件，包括为休斯顿地区的高中生提供构建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.