BRIGE: Tailoring Zeolite Crystallization Through Molecular Design

BRIGE：通过分子设计定制沸石结晶

• 批准号: 1032621
• 负责人: Jeffrey Rimer
• 金额: $ 17.5万
• 依托单位: University of Houston
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-09-01 至 2013-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1032621&HistoricalAwards=false
• 关键词: BRIGE; Tailoring; Zeolite; Crystallization; Through

1032621RimerDeveloping rational strategies for a priori tuning the self-assembly of ordered materials with predictable structural outcomes is a grand challenge in materials design, wherein few synthetic schemes of solid state materials are amenable to systematic and precise manipulation of crystal habit. In zeolite synthesis, engineering facile routes to precisely control crystal size and morphology is a benchmark for addressing systemic design limitations, which can marginalize their performance and economic viability in commercial applications. The objective of this proposed research plan is to develop a rational design strategy for manipulating the growth of ZSM-5, a ubiquitous zeolite catalyst, which is synthesized empirically with little fundamental understanding of crystallization. This BRIGE proposal will leverage the PI's expertise in crystal engineering and surface science to investigate ZSM-5 crystallization at an interfacial level, using atomic force microscopy to perform the following tasks: (i) pioneer in situ measurements of anisotropic growth kinetics; (ii) develop a design strategy using tailored modifiers with molecular recognition for binding to specific crystal faces and mediating growth; and (iii) monitor growth dynamics in real time to uncover the underlying mechanisms of self-assembly, which will facilitate the development of predictive models for tuning crystal habit. ZSM-5 is a promising catalyst for greenhouse gas emissions technologies due to its high activity for NOx reduction. The judicious modification of ZSM-5 crystal habit can alter porous surface area and internal diffusion pathlength, which regulate catalytic activity. Indeed, recent studies reveal that ultrathin ZSM-5 platelets, which are difficult to achieve by conventional syntheses, exhibit notably higher yield, selectivity, and lifetime. The successful completion of objectives in this research plan will provide a transformative approach to zeolite synthesis, and heuristic guidelines for design with potentially broader applicability to inorganic materials for viable applications in areas of energy and selective separations. The long-term trajectory of this research program aims to establish a comprehensive platform to design, model, and test zeolites for selective catalytic reduction (SCR) of NOx, using methane for on-board vehicle SCR technology development.Intellectual merit of the proposed activities: This proposed research will advance our fundamental understanding of zeolite crystallization, capitalizing on the PI's expertise in crystal engineering to apply AFM in ways that have not been utilized in zeolite science - namely in situ growth measurements to systematically quantify anisotropic kinetics, and force measurements to probe molecular recognition and binding at crystal interfaces. Molecular design principles of ZSM-5 will become a platform for addressing a broader range of zeolite structures, offering unprecedented control of crystal properties, which are unattainable by conventional methods. Long-term initiatives will institute synergistic collaborations with faculty at UH's Texas Diesel Testing and Research Center (TDTRC) to design and optimize zeolites for NOx CH4-SCR.Broader impact of the proposed activities: This BRIGE grant will help establish an outreach program at the K-12, undergraduate, and Ph.D. levels to promote engineering education and research, with emphasis on minority and female students through the PROMES and LSAMP programs at UH (whose minority enrollment ranks 2nd among national research universities). This plan will foster active learning through hands-on experience and classroom lectures, using concepts in crystallization to engage student interest in the sciences and increase awareness of interdisciplinary opportunities in engineering careers. The PI will partner with KIPP Houston High School (a minority institution ranked 16th in national college readiness) to establish a dynamic program for student and teacher (NSF-RET) research in the PI's lab and periodic guest lectures in KIPP's AP chemistry class. The PI will mentor NSF-REU, UH undergraduate and graduate research, using results of these studies as integrated topics in a colloids elective course.

1032621先验地调整具有可预测结构结果的有序材料的自组装的理性策略是材料设计中的巨大挑战，其中很少有固态材料的合成方案可以通过系统的和精确的水晶习惯操纵。在沸石合成中，精确控制晶体尺寸和形态的工程设施途径是解决系统性设计限制的基准，这可以使其在商业应用中的性能和经济可行性边缘化。该提出的研究计划的目的是制定一种合理的设计策略，以操纵ZSM-5的生长，ZSM-5（一种无处不在的沸石催化剂），该催化剂在经验上是合成的，对结晶的基本了解很少。这项BRIGE的建议将利用原子力显微镜执行以下任务来利用PI在晶体工程和表面科学方面的专业知识来研究ZSM-5结晶：（i）先驱原位测量各向异性生长动力学； （ii）使用具有分子识别的量身定制的修饰符制定设计策略，以结合特定的晶体面和介导生长； （iii）实时监测生长动力学，以发现自组装的潜在机制，这将促进调整晶体习惯的预测模型的发展。 ZSM-5是温室气体排放技术的有前途的催化剂，因为它的NOX减少活性很高。 ZSM-5晶体习惯的明智修饰可以改变多孔表面积和内部扩散路径长度，从而调节催化活性。确实，最近的研究表明，通过常规合成很难实现的超薄ZSM-5血小板表现出明显更高的产率，选择性和寿命。在本研究计划中，成功完成目标将为沸石合成提供一种变革性的方法，以及设计指南的设计指南，具有对无机材料的可能性更广泛的适用性，以在能源和选择性分离领域可行。该研究计划的长期轨迹旨在建立一个全面的平台，用于设计，模型和测试沸石，以选择性减少NOX的选择性催化性（SCR），并使用甲烷进行车载车载车辆SCR技术开发。拟议活动的智能优点：这项拟议的研究将提高我们对沸石结晶的基本理解，利用Pi在晶体工程方面的专业知识，以未在沸石科学中使用的方式应用AFM，即进行原位增长测量，即系统地量化各种动态动力学，并将其迫使测量。探针分子识别和在晶体界面上的结合。 ZSM-5的分子设计原理将成为解决更广泛的沸石结构的平台，从而提供了前所未有的晶体性能控制，这是通过常规方法无法实现的。长期举措将与UH的德克萨斯州柴油测试与研究中心（TDTRC）的教师建立协同合作，以设计和优化NOX CH4-SCR.Boader对拟议活动的影响：这项BRIGE GRAND将帮助建立在揭幕计划上K-12，本科和博士学位通过UH的舞会和LSAMP计划（其少数族裔入学率在国家研究大学中排名第二），以促进工程教育和研究，重点是少数群体和女学生。该计划将通过动手经验和课堂讲座来促进积极的学习，并使用结晶的概念来吸引学生对科学的兴趣并提高对工程职业中跨学科机会的认识。 PI将与Kipp Houston High School合作（少数族裔机构在全国大学准备中排名第16位），以在PI的实验室和Kipp AP Chemistry类中的定期来宾讲座上为学生和教师（NSF-RET）研究建立动态计划。 PI将使用这些研究的结果作为胶体选修课程中的综合主题来指导NSF-REU，UH本科和研究生研究。