Stimuli-Responsive Porous Molecular Crystals

刺激响应多孔分子晶体

基本信息

批准号：
1904998
负责人：
Ognjen Miljanic
金额：
$ 45.67万
依托单位：
University of Houston
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2019
资助国家：
美国
起止时间：
2019-08-15 至 2023-12-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904998&HistoricalAwards=false
关键词：
Stimuli Responsive Porous Molecular Crystals

项目摘要

Non-Technical AbstractAs part of this project, supported by the Solid State and Materials Chemistry program at NSF, Prof. Miljanic and his group develop and study new materials known as porous molecular crystals (PMCs). PMCs are solid crystals reminiscent of sponges: they have tiny pores, whose dimensions are comparable to those of molecules. In most currently known porous materials, pores are rigid in structure. In these new materials, pores are designed in a way which allows their shrinkage and expansion in response to changes in their environment. Specifically, the developed materials respond to high pressure and to exposure to gaseous chemicals, including environmental pollutants such as Freons and inhalation anesthetics. The resulting changes in pore dimensions are accompanied by changes in their optical properties (i.e. color under visible and ultraviolet light), and such modifications allow their use in the detection of environmental pollutants. Potential future applications of these pressure- and chemically responsive crystals are as shock absorbers, energy-storage materials, sensors, and materials that could catch-and-release chemicals-both harmful and useful ones-on demand. Additionally, societal benefits of this project include the education of a new generation of researchers at the interface of chemistry and materials science, and industry. Prof. Miljanic and coworkers have established a startup company which eventually could utilize the porous materials proposed in this work in the recycling of anesthetics. These efforts are complemented by curriculum enrichment at the University of Houston through the continued development of an upper-level undergraduate course on Energy and Sustainability, and the incorporation of 3D printing into chemistry curriculum.Technical AbstractThrough this project, supported by the Solid State and Materials Chemistry program at NSF, new classes of porous materials are prepared and studied. Porous molecular crystals (PMCs) are composed of discrete molecules which are held together in the solid state only by weak noncovalent interactions. These connections are flexible, allowing easy changes in the arrangement of PMCs constituents. As a result, it is anticipated that PMCs will be responsive to high pressures and guest entry into the pores, which the researchers are verifying experimentally. The pressure-based changes in the structures of PMCs are tracked through a combination of solid-state NMR spectroscopy, mercury intrusion porosimetry, and high-pressure crystallography at the Argonne National Laboratory. Because of their fluorescent character, such changes in pore dimensions are accompanied by visible and measurable changes in emission properties. This optical response can be used to prepare solid-state sensors for methanol and fluorinated refrigerants such as Freons, hydrofluorocarbons (HFCs), and hydrofluoroolefins (HFOs). As the final component of the work, new porous liquid crystals are synthesized and preliminarily studied. Their basis are shape-persistent macrocycles known as dehydrobenzannulenes, whose structures can sustain a columnar pore. Synthetic decoration of these columns with mesogenic groups translates into liquid crystalline behavior, which in turn is studied through a combination of methods involving both in-house and synchrotron techniques. Broader impacts of the proposed work are in the training of researchers at the interface of organic chemistry and materials science, utilization of PMCs as platforms for the recycling of anesthetics, and new curriculum offerings at the University of Houston, which include a course on Energy and Sustainability, and incorporation of 3D printing into chemistry instruction.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

NSF的固态和材料化学计划的支持，Miljanic教授及其小组开发和研究称为多孔分子晶体（PMCS）的新材料。 PMC是让人联想海绵的固体晶体：它们的毛孔很小，其尺寸与分子的尺寸相当。在目前大多数已知的多孔材料中，孔的结构刚性刚性。在这些新材料中，毛孔的设计方式可以使它们的收缩和扩展，以应对环境的变化。具体而言，开发的材料对高压和暴露于气态化学物质的反应，包括频率和吸入麻醉药等环境污染物。孔隙尺寸的结果变化伴随着其光学特性的变化（即在可见光和紫外线下的颜色），并且这种修饰允许它们用于检测环境污染物。这些压力和化学响应式晶体的潜在应用是减震器，能量储存材料，传感器和材料，这些材料和材料可能会捕捉和释放化学物质的有害和有用的需求。此外，该项目的社会益处包括在化学和材料科学以及行业的界面上对新一代研究人员的教育。 Miljanic教授及其同事建立了一家初创公司，该公司最终可以利用这项工作中提出的多孔材料，以回收麻醉药。通过持续开发有关能源和可持续性的高级本科课程，以及将3D打印纳入化学课程的课程，在休斯顿大学的课程充实得到了补充。技术抽象通过了该项目，由NSF的固态和材料化学计划支持NSF，NSF，新的Porous Materials的新项目支持。多孔分子晶体（PMC）由离散的分子组成，这些分子仅通过弱非共价相互作用在固态中结合在一起。这些连接是灵活的，可以轻松改变PMC成分的布置。结果，预计PMC将对高压和来宾进入毛孔有反应，研究人员正在通过实验进行验证。通过在Argonne National Laboratory的固态NMR光谱，汞入侵孔隙法和高压晶体学的组合结合使用基于压力的PMC结构的变化。由于其荧光特征，孔隙尺寸的这种变化伴随着可见的和可测量的发射特性变化。这种光学响应可用于制备用于甲醇和氟化制冷剂的固态传感器，例如Freons，Hydrofluorocarbons（HFCS）和Hydrofluoroolefins（HFOS）。作为工作的最终组成部分，合成并初步研究了新的多孔液晶。它们的基础是形状持久的大环，称为脱氢苯甲列烯，其结构可以维持柱状孔。与中源组的这些柱的合成装饰转化为液晶行为，这又通过涉及内部和同步加速器技术的方法的组合来研究。拟议工作的更广泛的影响是在有机化学和材料科学界面的研究人员中培训研究人员，将PMC作为麻醉剂回收的平台以及休斯敦的新课程提供的平台，包括能源和可持续性的课程，其中包括在化学教学中纳入4D印刷的指导。基金会的智力优点和更广泛的影响审查标准。

项目成果

期刊论文数量（9）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Selective chemisorption of polysulfides by porous molecular crystal: Cathode host materials for lean-electrolyte lithium-sulfur cells with high electrochemical stability

DOI：
10.1016/j.jpowsour.2023.232891
发表时间：
2023-05
期刊：
Journal of Power Sources
影响因子：
9.2
作者：
Yin-Ju Yen;Teng‐Hao Chen;Yao‐Ting Wang;Alexandra Robles;Miloš Đerić;O. Miljanić;Watchareeya Kaveevivitchai;Sheng‐Heng Chung
通讯作者：
Yin-Ju Yen;Teng‐Hao Chen;Yao‐Ting Wang;Alexandra Robles;Miloš Đerić;O. Miljanić;Watchareeya Kaveevivitchai;Sheng‐Heng Chung

Cyclotetrabenzil-Based Porous Organic Polymers with High Carbon Dioxide Affinity