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被用来提高化学反应速率，提高能效和对所需产品的直接反应。沸石是一类纳米型固酸催化剂，特别适合于天然气和石油资源衍生的碳氢化合物的反应。近年来，从基于化石的资源到可再生原料的过渡引发了人们对修饰沸石和其他微孔催化剂的兴趣，以提高其对原始生物质分子对高价值燃料和化学物质的反应的有效性。该项目研究了一种新的方法，用于修饰酸催化剂，涉及通过在狭窄空间中限制来促进反应速率，同时支持笨重的产物分子从活性位点扩散。该方法利用分子印记原子层沉积法来创建微孔二氧化硅结构附近，以在不施加运输约束的情况下诱导约束效应。这些具有可调多孔结构的固体酸催化剂将通过其在芳香醇和醛醇冷凝反应中的有效性和稳定性进行测试，这是因为它们在工业化学中的宽度应用以及升级生物量衍生分子而选择的。该项目将通过将研究结果整合到课堂材料中，为STEM中代表性不足的群体提供研究机会，为研究人员向当地K-12女学生展示了研究人员的实验室，并通过社交媒体渠道为研究人员创建和广播，这些研究人员的反应效果是核心研究，这是两种效果，从而确定了两种效果，从而使两种效果的研究涉及，从而使研究人员的实验室涉及两次，该项目将涉及研究结果和教育之间的牢固耦合。动力学以及观察到的速率，选择性和系统的运输，在诸如微孔酸性沸石之类的狭窄空间上发生的化学物质。然而，沸石材料中微孔结构的三维网络通常会引入不良的传输效应，从而导致孔隙阻塞引起的不希望的侧反应和催化剂失活。该项目的目的是通过开发和实施分子印记原子层沉积方法来添加另一个维度，以合理设计多孔材料，以在介孔铝硅硅酸盐的活跃地点附近创建微孔SIO2体系结构，以在不施加运输约束的情况下诱导隔热效果。这些具有可调多孔结构的固体酸将用于通过组合动力学，光谱和理论方法来评估其在观察速率，选择性和系统上的详细作用。为此，该提案旨在为主动站点操作提供全面的催化剂设计原则，以符合C-C耦合化学的特定要求。该奖项反映了NSF的法定任务，并被认为是通过基金会的知识分子优点和更广泛影响的评估标准来评估通过评估来获得的支持。