CAREER: Molecular imprinting strategy to rationally design porous solid acid catalysts for C-C coupling chemistries

职业：分子印迹策略合理设计用于 C-C 偶联化学的多孔固体酸催化剂

• 批准号: 2340993
• 负责人: Stephanie Kwon
• 金额: $ 65.68万
• 依托单位: Colorado School of Mines
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-01-15 至 2028-12-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2340993&HistoricalAwards=false
• 关键词: CAREER; Molecular; imprinting; strategy; rationally

Catalysts have long been used to enhance the rate of chemical reactions, improve energy efficiency, and direct reactions toward desired products. Zeolites are a class of nanoporous solid-acid catalysts that are particularly well suited to reactions of hydrocarbons derived from natural gas and petroleum resources. The transition from fossil-based resources to bio-renewable feedstocks in recent years has triggered interest in modifying zeolites and other microporous catalysts to increase their effectiveness for reacting raw biomass molecules to higher-value fuels and chemicals. The project investigates a novel approach for modifying acid catalysts that involves promoting reaction rates through confinement in tight spaces while facilitating diffusion of bulky product molecules away from the active sites. The approach utilizes a molecular imprinting atomic layer deposition method to create microporous silica structures near the active sites to induce confinement effects without imposing transport constraints. These solid acids catalysts with tunable porous structures will be tested for their effectiveness and stability in aromatic alkylation and aldol condensation reactions, chosen because of their widespread application in industrial chemistry and in upgrading biomass-derived molecules. The project will involve strong coupling between research and education by integrating the research results into classroom materials, providing research opportunities for students from historically underrepresented groups in STEM, showcasing the investigator’s laboratories to local K-12 female students, and creating and broadcasting educational videos via social media channels for researchers who are new to heterogeneous catalysis research.Over the last two decades, the field has made significant progress in understanding the effects of reaction network, kinetics, and transport on observed rates, selectivities, and stabilities, on chemistries occurring on confined spaces such as microporous acidic zeolites. Yet, the three-dimensional network of microporous structures in zeolitic materials often introduces unwanted transport effects that can lead to undesired side reactions and catalyst deactivation caused by pore blockage. This project aims to add another dimension in rationally designing porous materials by developing and implementing molecular imprinting atomic layer deposition methods to create microporous SiO2 architecture near active sites in mesoporous aluminosilicates to induce confinement effects without imposing transport constraints. These solid acids with tunable porous structures will be used to assess their detailed role on observed rates, selectivities, and stabilities by combining kinetic, spectroscopic, and theoretical methods. In doing so, this proposal aims to provide comprehensive catalyst design principles for active site manipulation that match the specific requirements of C-C coupling chemistries.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.

催化剂长期以来一直用于提高化学反应速率、提高能源效率以及直接反应生成所需产品。沸石是一类纳米多孔固体酸催化剂，特别适合来自天然气和石油资源的碳氢化合物的反应。近年来，从化石资源到生物可再生原料的转变引发了人们对改性沸石和其他微孔催化剂的兴趣，以提高其将原始生物质分子反应成更高价值的效率。该项目研究了一种改进酸催化剂的新方法，该方法包括通过限制在狭小的空间中提高反应速率，同时促进大体积产物分子扩散远离活性位点。该方法利用分子印迹原子层沉积方法来创建微孔。将测试这些具有可调多孔结构的固体酸催化剂在活性位点附近诱导限制效应的有效性和稳定性。由于其在工业化学和生物质衍生分子升级方面的广泛应用，该项目将通过将研究成果整合到课堂材料中，将研究与教育紧密结合起来，为来自 STEM 历史上代表性不足的群体的学生提供研究机会，展示研究者的研究成果。实验室向当地 K-12 女学生提供帮助，并通过社交媒体渠道为刚接触多相催化研究的研究人员制作和播放教育视频。在过去的二十年中，该领域在理解反应网络的影响方面取得了重大进展，然而，沸石材料中微孔结构的三维网络通常会引入不需要的传输效应，从而导致不希望的副反应。该项目旨在通过开发和实施分子印迹原子层沉积方法来创建微孔，为合理设计多孔材料增加另一个维度。介孔硅铝酸盐活性位点附近的 SiO2 结构可在不施加传输限制的情况下诱导限制效应。这些具有可调多孔结构的固体酸将用于通过结合动力学、光谱和理论方法来评估其对观察速率、选择性和稳定性的详细作用。为此，该提案旨在为活性位点操作提供全面的催化剂设计原则，以满足 C-C 偶联化学的具体要求。该奖项反映了 NSF 的法定使命，并被认为是值得的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来提供支持。