UNS:Designing Metal-Exchanged Zeolites with Improved Activity, Selectivity and Stability for Non-Oxidative Methane Upgrade

1512224（Rimer）该研究解决了催化研究的一个关键领域——将甲烷转化为更高价值的产品——这是由于美国大量页岩气资源的出现，以及避免天然气燃烧、将天然气转化为更高价值、可运输、燃料和化学产品的商业和环境激励。沸石催化是甲烷升级的一种潜在途径。本研究将利用实验方法和理论工具，重点研究性能改进的新型沸石催化剂的设计。这项工作将沸石合成和表征、动力学研究和密度泛函数理论计算方面的专业知识结合起来，设计出具有提高产品收率和耐久性的金属交换沸石，通过非氧化偶联和脱氢芳烃两种过程进行非氧化甲烷升级。为此，工作将集中在与刘易斯酸度（与不同交换金属相关）、约束效应、沸石框架的选择以及混合金属沸石的理论指导筛选方案相关的4个具体目标上。考虑到沸石结构中反应的复杂性和反应环境，合成、表征和理论之间的联系尤其需要在沸石基甲烷升级方面取得重大进展。页岩气的大量出现极大地改变了天然气资源的商业和环境格局。目前，大部分偏远地区的天然气被燃烧，产生大量的二氧化碳——温室气体清单的主要贡献者。迫切需要将甲烷转化为高价值液体燃料和化学产品的直接工艺。然而，催化挑战是艰巨的。该建议将解决目前的技术差距，并将为未来在沸石基甲烷转化工艺领域的研究提供理论基础。为此，它有可能大大提高我们对直接催化甲烷升级相关挑战的理解，以及沸石基催化技术在克服这些挑战方面的潜在应用。pi还将对各级学生进行教育和推广计划，以提高对STEM学科在解决能源相关问题中的作用的认识。

1512224(Rimer)The study addresses a critical area of catalysis research - upgrading of methane to higher value products - brought on by the emergence of large quantities of shale gas resources in the United States, along with both commercial and environmental incentives to avoid gas flaring and instead convert the gas to higher value, transportable, fuel and chemical products. Zeolite catalysis represents a potential path to methane upgrading. The study will focus on the design of new zeolite catalysts with improved capability, utilizing both experimental methods and theoretical tools. The proposed work brings together expertise in zeolite synthesis and characterization, kinetic studies, and density functional theory calculations to design metal-exchanged zeolites with improved product yield and durability for non-oxidative methane upgrading via two processes: non-oxidative coupling and dehydroaromtization. To this end the work will focus on 4 specific aims related to Lewis acidity (associated with different exchanged metals), confinement effects, choice of zeolite framework, and a theory-guided screening protocol for mixed metal zeolites. Given the complexity of the reactions and the reaction environment within the zeolite structures, the linkage between synthesis, characterization and theory is especially needed for significant advances to be made in zeolite-based methane upgrading. The emergence of large quantities of shale gas has dramatically changed the commercial and environmental landscape for natural gas resources. Much of the remote gas is presently flared with the production of large quantities of carbon dioxide - a major contributor to the greenhouse gas inventory. Direct processes for converting methane to higher value liquid fuel and chemical products are sorely needed. Yet the catalytic challenge is daunting. This proposal will address the current gap in technology and will provide a theoretical basis for future research in the area of zeolite-based methane conversion processes. To this end, it has potential to significantly advance our understanding of both the challenges associated with direct catalytic methane upgrading and the potential utility of zeolite-based catalysis for overcoming those challenges. The PIs will also conduct education and outreach programs to students at all levels to raise awareness of the role of STEM disciplines in addressing energy-related issues.