RUI: New Ultrastable Crystalline Porous Materials

RUI：新型超稳定结晶多孔材料

• 批准号: 2105961
• 负责人: Xianhui Bu
• 金额: $ 39.2万
• 依托单位: California State University-Long Beach Foundation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2105961&HistoricalAwards=false
• 关键词: RUI; New; Ultrastable; Crystalline; Porous

NON-TECHNICAL SUMMARYMetal-organic frameworks are molecular-scale sieves composed of metal centers coordinated to organic ligands, which results in three-dimensional structures with uniform pore size. They can enable or improve large-scale energy, health, and defense applications such as gas storage and separation, water and other chemical decontamination, direct water harvesting and carbon dioxide capture from air, and nuclear waste treatment. However, currently few metal-organic framework materials have a suitable combination of porosity and chemical stability to meet the demands of these applications. Developing chemically stable and pore-size-tunable metal-organic frameworks is among the most important scientific challenges and is the objective of this project, which is supported by the Solid State and Materials Chemistry program in the Division of Materials Research. The project aims to impart high chemical stability by simultaneously creating highly connected structural building blocks and rigid frameworks that are not easily broken down by common molecules and molecular fragments, such as water and hydroxide ions. The pore geometry of these new materials can be tuned using different combinations structural building blocks and organic ligands. By developing these new synthesis pathways new materials with the highest chemical stability among metal-organic framework materials are created that can be used under harsh chemical conditions commonly encountered in real-world applications. In addition, this project enables a variety of research activities and provides rich training opportunities for a diverse population of undergraduate and graduate students at California State University – Long Beach.TECHNICAL SUMMARYWith this project, supported by the Solid State and Materials Chemistry program in the Division of Materials Research, Prof. Xianhui Bu and his research group develop synthetic pathways to create a family of new ultrastable and ultratunable metal-organic framework materials. The structural platform has an extraordinary flexibility in metal-ligand bond type (e.g., metal-carboxylate, metal-azolate, metal-pyridyl), which allows a high level of control over porosity, functionality, and stability within the same isoreticular series of materials. To expand the boundaries in acid-base stability of metal-organic frameworks, the researchers synthesize chromium-trimer-based frameworks with the high-connected (higher than 6) trimer building block. Only low-connected chromium metal-organic frameworks (6 or less) were known prior to this project, and the creation of high-connected framework materials in this project with mixed Cr-O and Cr-N crosslinks further increases the kinetic inertness of trivalent metal ions and also shields the metal nodes from chemical attacks by coordinating species. The researchers also systematically explore key experimental parameters such as reaction temperature, solvent type, and modulators, all of which play a far greater role for nonlabile metal ions in this project, compared to labile ions in most metal-organic frameworks. The integrated compositional and structural features to be achieved in this project increase acid-base stability simultaneously in both low- and high-pH directions. The exceptional chemical stability of these materials can enable a broad range of applications, especially those that operate under harsh chemical conditions such as nuclear waste treatment. In addition, this project enables a variety of research activities and provides rich training opportunities for a diverse population of undergraduate and graduate students at California State University – Long Beach.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.

非技术摘要金属有机骨架是由与有机配体配位的金属中心组成的分子级筛，其产生具有均匀孔径的三维结构，它们可以实现或改善大规模的能源、健康和国防应用，例如。气体储存和分离、水和其他化学净化、直接集水和从空气中捕获二氧化碳以及核废料处理。然而，目前很少有金属有机骨架材料具有合适的孔隙率和化学稳定性组合。满足这些应用的需求是最重要的科学挑战之一，也是该项目的目标，该项目得到了固体与材料化学部门的支持。材料研究。该项目旨在通过同时创建不易被常见分子和分子碎片（例如水和氢氧根离子）分解的高度连接的结构构件和刚性框架来赋予高化学稳定性。是通过开发这些新的合成途径，可以创建金属有机骨架材料中化学稳定性最高的新材料，这些材料可以在实际应用中常见的恶劣化学条件下使用。 ，该项目支持各种研究活动，并为加州州立大学长滩分校的不同人群的本科生和研究生提供丰富的培训机会。技术摘要该项目得到了材料系固态和材料化学项目的支持研究，教授。卜贤辉和他的研究小组开发了一系列新型超稳定和超可调金属有机骨架材料的合成途径，该结构平台在金属-配体键类型（例如金属-羧酸盐、金属-氮唑盐、金属-配体键）方面具有非凡的灵活性。吡啶基），它可以对同一等网状系列材料的孔隙率、功能性和稳定性进行高水平的控制，为了扩大金属有机框架的酸碱稳定性的界限，研究人员。在该项目和高连接框架的创建之前，仅已知低连接铬金属有机框架（6或更少）与高连接（高于6）三聚体构建块合成基于铬三聚体的框架。该项目中的材料具有混合Cr-O和Cr-N交联，进一步提高了三价金属离子的动力学惰性，并通过配位物种保护金属节点免受化学攻击。与大多数金属有机框架中的不稳定离子相比，反应温度、溶剂类型和调节剂等关键实验参数对本项目中的非不稳定金属离子发挥着更大的作用。该项目同时提高了低 pH 值和高 pH 值方向的酸碱稳定性，这些材料卓越的化学稳定性可实现广泛的应用，特别是在核废料处理等恶劣化学条件下运行的应用。 ，该项目能够进行各种研究该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。