UNS:Predictive Ab Initio Dynamics in Zeolite Biofuel Production Catalysts: Towards More Gas and Less Coke

奥尔巴赫(1512442)-这项研究涉及理论计算，旨在了解在沸石的受限空间中将生物质衍生的有机化合物转化为液体燃料前体所涉及的复杂催化，同时避免因结焦而导致的失活。将采用一种新的理论方法，以实验数据为基准。PI还将把他的研究纳入教育和推广项目，包括为初中和高中女孩提供身临其境的暑期科学体验。该建议建立在认识到生物质衍生的有机物种选择性地转化为更长链的液体燃料前体和不希望看到的反应形成焦炭这两个例子都是碳-碳键形成反应的例子，因此服从于理论方法，这些方法提供了对分子筛结构和化学性质影响的碳链增长的基本机制的洞察。因此，拟议的工作解决了这两种现象，但通过一种独特的理论方法-“反向元动力学”-通过检查更直接的碳-碳键断裂过程并呼吁微观可逆性来洞察碳加成反应。为此，PI将使用和扩展他的实验室(与软件公司Schroedinger合作)开发的计算催化的多个方面，以获得碳键形成和断裂的准确能量，同时纳入框架动力学和长程力的影响，同时保持模拟时间可控。具体地说，这项工作将解决沸石笼中的限制效应如何影响Aldol缩合反应中活化和缩合步骤之间的平衡。理论预测将以他的合作者Paul Dauenhaer进行的相关实验研究为基准。这项研究的更广泛影响在于它将提供对沸石结构中的有机反应的总体洞察，特别是控制缩合反应之间的选择性以产生所需的特定碳数产物和无节制的碳缩合形成焦炭的因素。除了对Aldol缩合过程的直接了解外，将开发和完善的理论技术应该对沸石笼受限环境中的反应过程具有广泛的适用性。PI制定了一项强有力的教育和推广计划，纳入了他的研究的各个方面，同时解决了一些研究表明，女孩在中学阶段对科学和数学的兴趣下降。他还领导着一个面向麻省理工学院本科生的跨学科项目，该项目由学生组成团队，解决现实世界的科学问题，特别是与生物医学和可再生能源有关的问题。

Auerbach (1512442) - The study involves theoretical calculations aimed at understanding the complex catalysis involved in converting biomass-derived organic compounds to liquid fuel precursors in the confined spaces of zeolites while avoiding deactivation due to coke formation. A novel theoretical approach will be employed that will be benchmarked against experimental data. The PI will also incorporate aspects of his research into educational and outreach programs including an immersive summer science experience for middle- and high-school girls.The proposal builds on recognition that selective conversion of biomass-derived organic species to longer-chain liquid fuel precursors and the undesired reaction to form coke, are both examples of carbon-carbon bond forming reactions, and thus amenable to theoretical methods that provide insight into fundamental mechanisms of carbon chain growth as affected by zeolite structure and chemical properties. Thus, the proposed work addresses both phenomena, but through a unique theoretical approach - "metadynamics in reverse" - by examining the more-straightforward carbon-carbon bond breaking process and appealing to microscopic reversibility to gain insight into the carbon addition reactions. To this end, the PI will employ and extend several aspects of computational catalysis developed in his lab (in collaboration with the software firm SCHROEDINGER) to obtain accurate energetics of carbon bond forming and breaking while incorporating effects of framework dynamics and long-range forces, all while keeping simulation times manageable. Specifically, the work will address how confinement effects in the zeolite cage influence the balance between the activation and condensation steps in aldol condensation. The theoretical predictions will be benchmarked against related experimental studies carried out by his collaborator, Paul Dauenhauer.The broader impact of the research is in the general insight it will provide on organic reactions in zeolite structures, especially the factors that control selectivity between condensation reactions to produce desired specific carbon-number products and unchecked carbon condensation to form coke. In addition to the direct insight into the aldol condensation process, the theoretical techniques that will be developed and refined should have broad applicability to reaction processes in the confined environment of zeolite cages. The PI has developed a strong education and outreach plan that incorporates aspects of his research while addressing studies showing that interest in science and math dwindles amongst girls during their middle-school years. He also directs an inter-disciplinary program for undergraduate students at U Mass Amherst that forms teams of students to address real-world scientific issues, especially those dealing with biomedicine and renewable energy.