CAREER: Zwitterionic Metal-Organic Frameworks with Multi-Stimulus-Responsive Properties

职业：具有多刺激响应特性的两性离子金属有机框架

• 批准号: 1752771
• 负责人: Mario Wriedt
• 金额: $ 59.27万
• 依托单位: Clarkson University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-03-01 至 2025-02-28
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1752771&HistoricalAwards=false
• 关键词: CAREER; Zwitterionic; Metal; Organic; Frameworks

Non-technical Abstract:This CAREER project is an integrated research, education, and outreach program funded by the Solid-State and Materials Chemistry program of the Division of Materials Research. The overall goal of the research plan is to devise strategies that enable the synthesis of a new class of advanced porous materials composed of charge-separated molecular building blocks. These charges can perform a desired function to attract specific guest molecules within the material's pores. In one line of research, the ability of light to interact with these charges will be explored to trigger the release of guest molecules to determine if the material can be regenerated to its original state. This feature would be particularly useful for a multitude of environmental applications that seek the adsorption or separation of gases, such as hydrogen storage and carbon capture respectively with the general objective to counteract global warming. Leveraging the research activities is the educational plan that will allow Clarkson University to offer a stronger, ACS-approved chemistry program, the foundation for a broad, rigorous chemistry education that provides students with the intellectual, experimental, and communication skills to become effective professionals. The outreach program is hands-on and incorporates state-of-the-art crystallography instrumentation to significantly strengthen and expand the high school to college pipeline for students from the rural North Country of New York State by increasing their exposure to and interest in STEM fields and careers. An X-ray diffraction workshop will provide participants with the training to understand and appropriately utilize the most precise method of determining crystal structures, thus allowing the analysis of fundamental structure-property relationship.Technical Abstract:The proposed research plan addresses fundamental questions essential to the advancement of functional porous materials with multi-stimulus-responsive adsorption properties and rapid controllable release of guest molecules. Proposed is the use of zwitterionic metal-organic framework (ZW MOF) building blocks whose molecular surfaces show well-separated intramolecular charges with tunable electric field gradients. These gradients present potential multi-point adsorption sites that can be designed at a molecular level within the zwitterionic ligands prior to MOF self-assembly. Once zwitterions are incorporated into MOFs, their electric field gradients yield charged organic surfaces (COSs) within the pores, which in turn polarize guest molecules, resulting in defined adsorption properties. The most important feature of zwitterions is their sensitivity to external stimuli (e.g. light or electrochemical), resulting in switchable COSs that enable significant control and tunability of adsorption properties. Specific approaches are to: (1) Design and investigate ZW ligands as a new, simple, and controllable means to introduce COSs into pore linings to create MOFs with defined host-guest interactions; (2) Explore post-synthetic modification reactions as alternative routes for introducing ZW functionalities into MOFs; and (3) Demonstrate and optimize the multi-stimulus-responsive tunability of COSs by controllable release of guest molecules from MOF pores. These experiments will ultimately provide a powerful tool to tailor MOFs with tunable host-guest interactions and will generate fundamental knowledge on a novel type of multi-stimulus-responsive material with distinct adsorption and desorption properties.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.

非技术性摘要：这个职业项目是一个综合的研究、教育和推广项目，由材料研究部的固态和材料化学项目资助。该研究计划的总体目标是设计出能够合成由电荷分离分子构建块组成的新型先进多孔材料的策略。这些电荷可以执行预期的功能，将特定的客体分子吸引到材料的孔隙中。在一项研究中，将探索光与这些电荷相互作用的能力，以触发客体分子的释放，以确定材料是否可以再生到其原始状态。这一特征对于寻求吸附或分离气体的多种环境应用特别有用，例如分别以抵消全球变暖为总体目标的氢气储存和碳捕获。利用研究活动的教育计划将使克拉克森大学能够提供更强大的、经ACS批准的化学课程，为广泛而严格的化学教育奠定基础，为学生提供智力、实验和沟通技能，以成为有效的专业人员。该推广计划是亲身实践的，结合了最先进的结晶学仪器，通过增加学生对STEM领域和职业的接触和兴趣，显著加强和扩大了来自纽约州北部农村地区的学生从高中到大学的渠道。X射线衍射工作坊将为学员提供了解和适当使用最精确的确定晶体结构的方法的培训，从而允许分析基本的结构-性质关系。技术摘要：拟议的研究计划解决了对具有多刺激响应吸附特性和快速可控释放客体分子的功能多孔材料的进步至关重要的基本问题。提出了使用两性离子金属-有机骨架(ZW MOF)构筑块，其分子表面显示出具有可调电场梯度的分子内电荷。这些梯度提供了潜在的多点吸附位置，可以在分子水平上在MOF自组装之前在两性离子配体内进行设计。一旦两性离子被结合到MOF中，它们的电场梯度在孔内产生带电的有机表面(COS)，进而使客体分子极化，从而产生明确的吸附性能。两性离子最重要的特征是它们对外界刺激(如光或电化学)的敏感性，从而产生可切换的CO，从而实现显著的吸附性能控制和可调。具体的方法是：(1)设计和研究ZW配体作为一种新的、简单和可控的方法将COS引入孔衬里以创建具有明确主客体相互作用的MOF；(2)探索合成后修饰反应作为将ZW功能引入MOF的替代途径；以及(3)通过可控地从MOF孔中释放客体分子来展示和优化COS的多刺激响应可调性。这些实验最终将提供一个强大的工具来定制具有可调主-客相互作用的MOF，并将产生关于具有独特吸附和解吸特性的新型多刺激响应材料的基础知识。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Metal-organic frameworks as platforms for the removal of per- and polyfluoroalkyl substances from contaminated waters

• DOI: 10.1016/j.matt.2022.07.028
• 发表时间: 2022-10
• 期刊: Matter
• 影响因子: 18.9
• 作者: Rui Li;N. N. Adarsh-N.;Hui Lu;Mario Wriedt

CO 2 Capture: Dry and Wet CO 2 Capture from Milk‐Derived Microporous Carbons with Tuned Hydrophobicity (Adv. Sustainable Syst. 11/2020)

CO 2 捕获：从牛奶中干法和湿法捕获 CO 2 — 具有调节疏水性的衍生微孔碳（Adv. Sustainable Syst. 11/2020）

• DOI: 10.1002/adsu.202070022
• 发表时间: 2020
• 期刊: Advanced Sustainable Systems
• 影响因子: 7.1
• 作者: Pokrzywinski, Jesse;Aulakh, Darpandeep;Verdegaal, Wolfgang;Pham, Viet Hung;Bilan, Hubert;Marble, Sam;Mitlin, David;Wriedt, Mario
• 通讯作者: Wriedt, Mario

Rational Design of Pore Size and Functionality in a Series of Isoreticular Zwitterionic Metal–Organic Frameworks

• DOI: 10.1021/acs.chemmater.8b03885
• 发表时间: 2018-10
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: Darpandeep Aulakh;Timur Islamoglu;Veronica F. Bagundes;Juby R. Varghese;Kyle Duell;Monu Joy;S. Teat