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.

1032621Rimer开发合理的策略来先验地调整有序材料的自组装，并具有可预测的结构结果，这在材料设计中是一个巨大的挑战，因为很少有固态材料的合成方案能够系统和精确地操纵结晶习惯。在沸石合成中，精确控制晶体大小和形貌的工程简便方法是解决系统性设计限制的基准，这些限制可能会使其在商业应用中的性能和经济可行性被边缘化。这项拟议的研究计划的目标是开发一种合理的设计策略来控制ZSM-5的生长，ZSM-5是一种普遍存在的沸石催化剂，它是在对结晶几乎没有基本了解的情况下通过经验合成的。这项Brige建议将利用PI在晶体工程和表面科学方面的专业知识，在界面水平上研究ZSM-5结晶，使用原子力显微镜来执行以下任务：(I)首创各向异性生长动力学的原位测量；(Ii)开发使用具有分子识别功能的定制修饰剂的设计策略，以结合到特定的晶面并调节生长；以及(Iii)实时监测生长动力学，以揭示自组装的潜在机制，这将有助于开发用于调整晶体习惯的预测模型。ZSM-5分子筛具有较高的NOx还原活性，是一种很有前途的温室气体排放催化剂。对ZSM-5分子筛的晶性进行适当的修饰，可以改变催化剂的孔表面积和内扩散路径长度，从而调节催化剂的活性。事实上，最近的研究表明，超薄的ZSM-5血小板，很难通过传统的合成方法获得，表现出显著更高的产率、选择性和寿命。本研究计划目标的成功完成将为沸石合成提供一种变革性的方法，并为设计具有潜在更广泛适用性的无机材料在能源和选择性分离领域的可行应用提供启发式指导方针。这项研究计划的长期目标是建立一个全面的平台来设计、建模和测试用于NOx选择催化还原(SCR)的沸石，利用车载甲烷选择性催化还原(SCR)技术开发。拟议活动的智力优点：这项拟议的研究将促进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沸石科学中尚未使用的方式应用AFM-即原位生长测量以系统量化各向异性动力学，以及强制测量以探测分子在晶体界面的识别和结合。ZSM-5的分子设计原理将成为解决更广泛沸石结构的平台，提供前所未有的晶体性质控制，这是传统方法无法实现的。长期计划将与UH的德克萨斯柴油测试和研究中心(TDTRC)的教职员工进行协同合作，为NOx CH4-SCR设计和优化沸石。布罗德拟议活动的影响：这项布里奇拨款将帮助建立一个K-12、本科生和博士级别的扩展计划，以促进工程教育和研究，重点是通过UH的PROMES和LSAMP计划(其少数族裔招生人数在全国研究型大学中排名第二)针对少数族裔和女性学生。该计划将通过实践经验和课堂讲授培养学生的主动学习能力，利用正在形成的概念来激发学生对科学的兴趣，并提高对工程职业中跨学科机会的认识。PI将与KIPP休斯顿高中(一所在全国大学准备度排名第16的少数族裔学校)合作，在PI的实验室建立学生和教师研究(NSF-RET)的动态计划，并定期在KIPP的AP化学课堂上进行客座讲座。PI将指导NSF-REU、密歇根大学本科生和研究生研究，将这些研究的结果作为胶体选修课的综合主题。