Carbon-based nanocomposites for sensing and catalysis

用于传感和催化的碳基纳米复合材料

• 批准号: 2207299
• 负责人: Timothy Swager
• 金额: $ 72.84万
• 依托单位: Massachusetts Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-01 至 2026-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2207299&HistoricalAwards=false
• 关键词: Carbon; based; nanocomposites; sensing; catalysis

Non-Technical Summary: Carbon-based electronic nanocomposites offer new opportunities to improve the environment by enabling sensors and improving processes that underpin the materials used in our day-to-day existence. Harnessing this potential requires deep understanding of the reactivity of these materials and new methods to create composite materials with novel functionalities. Chemists have a great understanding of the reactivity of small molecules in solution in a homogenous environment. With support from the Solid State and Materials Chemistry program in the Division of Materials Research and the Catalysis program in the Division of Chemistry, this research seeks to extend the known precision of small molecules to carbon-based nanomaterials, which have much more complex structures and solid-state organizations. Translating homogenous reactivity concepts for catalysis and sensing is accomplished by building on new methods for attaching structures to or assembling structures around carbon nanomaterials. For example, carbon-based nanomaterials can support metal catalysts when materials that actively bind the metals are part of the assembled compositions. Researchers at the Massachusetts Institute of Technology develop new methods that deliver electrons on demand to drive reactions in more efficient and selective processes. For example, in many cases in catalysis, rare metals such as platinum are needed. This is particularly true in catalysis needed for energy conversion technologies. This research creates supporting nanomaterials that allow for superior reactivity with much smaller quantities of these valuable materials. This effort also supports educational opportunities to diversify the STEM workforce through an exchange program between Massachusetts Institute of Technology and minority serving institutions, and to inspire new generations of scientists in both research and business careers. Technical Summary: With support from the Solid State and Materials Chemistry program in the Division of Materials Research and the Catalysis program in the Division of Chemistry, this research seeks to create multi-component functional materials systems from graphene, carbon nanotubes (CNTs), metal nanoparticles, and porous polymers. It leverages new methods for the covalent functionalization of graphene surfaces and confined cavities in porous polymers to produce highly active small ( 5 nm diameter) metal nanoparticles of controlled composition. Covalent modification of the sidewalls of carbon nanotubes is used as a method to “hard wire” molecular catalytic species to a conductive element and produce high catalytic activity and this approach will be expanded to the generation of asymmetric electrocatalysis. The electrophilic metal-oxo intermediates generated in the oxygen evolution reaction is used to react with alkenes for electrochemical epoxidation and chiral CNT-catalysts are employed to generate optically active epoxides. The researchers covalently functionalize carbon nanotubes and carbon nanotubes coated with porous poly(phenylene ether)s (PAEs) that contain metal binding ligands, which allows them to investigate reductive coupling of aryl-halides by Ni(0) in such conducting supports. Developing new synthetic methods for PAE opens up the scope of possibilities and a diversity of metal binding ligands can be included in the polymer. The principal investigator and his team also study whether porous ligands containing PAEs could be used to deliver only a single metal center to each NP with the balance of the composition containing one or more other earth abundant metals. Multi-elemental NP compositions are explored to create catalysts for fuel cell relevant reactions, including ethanol oxidation, hydrogen oxidation, and oxygen reduction as well as new chemiresistive sensors. Porous PAEs with integrated dyes are investigated as photoredox catalytic systems, in particular to determine if asymmetric PAE pockets can produce chiral products. In addition to advancing fundamental materials chemistry and potentially producing new commercially relevant technologies, this research also supports educational opportunities to diversify the workforce and inspire new generations of scientists in both research and business careers.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：碳基电子纳米复合材料通过启用传感器和改进支撑我们日常生活中使用的材料的工艺，为改善环境提供了新的机会。要利用这种潜力，需要深入了解这些材料的反应性和性能。在材料研究和催化部门的固态和材料化学项目的支持下，化学家对均匀环境中小分子的反应性有了深入的了解。作为化学系的一个项目，这项研究旨在将已知的小分子精度扩展到碳基纳米材料，这些材料具有更复杂的结构和固态组织，通过建立新的基础来实现催化和传感的均质反应概念。例如，当主动结合金属的材料是组装组合物的一部分时，碳基纳米材料可以支持金属催化剂。例如，在催化过程中，许多情况下需要铂等稀有金属，这在能量转换技术所需的催化作用中尤其如此。这项努力还通过麻省理工学院和少数族裔服务机构之间的交流计划，支持教育机会，使 STEM 劳动力多样化，并激励新一代科学家从事研究和商业职业。 .技术概要：在材料研究部固态与材料化学项目和化学部催化项目的支持下，本研究旨在利用石墨烯、碳纳米管（CNT）、金属纳米粒子和它利用石墨烯表面和多孔聚合物中的有限空腔的共价功能化的新方法来生产成分受控的高活性小（直径 5 nm）金属纳米粒子。碳纳米管侧壁的共价修饰被用作一种“硬线生产”分子催化物种到导电元素和高催化活性的方法，并且这种方法将扩展到不对称电催化生成的亲电金属-氧中间体。研究人员使用析氧反应中的碳纳米管与烯烃进行电化学环氧化反应，并利用手性碳纳米管催化剂共价生成光学活性环氧化物。对碳纳米管和涂有含有金属结合配体的多孔聚苯醚（PAE）的碳纳米管进行功能化，这使他们能够研究此类导电载体中 Ni(0) 与芳基卤化物的还原偶联，从而开发新的合成方法。 PAE 开辟了可能性，聚合物中可以包含多种金属结合配体。首席研究员和他的团队还研究了含有 PAE 的多孔配体是否可用于仅传递单一金属。探索多元素纳米颗粒组合物以制造燃料电池相关反应的催化剂，包括乙醇氧化、氢氧化和氧还原以及新的化学电阻。具有集成染料的多孔 PAE 被作为光氧化还原催化生产系统进行研究，特别是为了确定不对称 PAE 口袋是否可以产生手性产物，以及推进基础材料化学并可能生产新的产品。这项研究不仅涉及商业相关技术，还支持教育机会，使劳动力多样化，并激励新一代科学家从事研究和商业职业。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进行评估，被认为值得支持审查标准。

项目成果

Electrocatalytic Isoxazoline–Nanocarbon Metal Complexes

电催化异恶唑啉纳米碳金属配合物

• DOI: 10.1021/jacs.1c05439
• 发表时间: 2021-07
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Luo, Shao;Liu, Richard Y.;Lee, Sungsik;Swager, Timothy M.
• 通讯作者: Swager, Timothy M.

Methane Detection with a Tungsten‐Calix[4]arene‐Based Conducting Polymer Embedded Sensor Array

使用钨-Calix[4]芳烃-基导电聚合物嵌入式传感器阵列检测甲烷

• DOI: 10.1002/adfm.202007281
• 发表时间: 2020-11
• 期刊: Advanced Functional Materials
• 影响因子: 19
• 作者: Lu, Ru‐Qiang;Luo, Shao‐Xiong Lennon;He, Qilin;Concellón, Alberto;Swager, Timothy M.
• 通讯作者: Swager, Timothy M.

Chemiresistive Hydrogen Sensing with Size-Limited Palladium Nanoparticles in Iptycene-Containing Poly(arylene ether)s

在含异丙苯的聚亚芳基醚中使用尺寸有限的钯纳米颗粒进行化学电阻式氢传感

• DOI: 10.1021/acsnano.2c10736
• 发表时间: 2023-02
• 期刊: ACS Nano
• 影响因子: 17.1
• 作者: Luo, Shao;Yuan, Weize;Xue, Mantian;Feng, Haosheng;Bezdek, Máté J.;Palacios, Tomás;Swager, Timothy M.
• 通讯作者: Swager, Timothy M.

Versatile Nanoporous Organic Polymer Catalyst for the Size-Selective Suzuki–Miyaura Coupling Reaction

用于尺寸选择性 Suzuki-Miyaura 偶联反应的多功能纳米多孔有机聚合物催化剂

• DOI: 10.1021/acsanm.2c04393
• 发表时间: 2022-12-05
• 期刊: ACS Applied Nano Materials
• 影响因子: 5.9
• 作者: Shengjin Guo;Yifan Wu;Shao;T. Swager
• 通讯作者: T. Swager