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

1512224（Rimer）该研究涉及催化研究的一个关键领域-甲烷升级为更高价值的产品-由美国大量页岩气资源的出现带来，沿着商业和环境激励措施，以避免天然气燃烧，而是将天然气转化为更高价值，可运输的燃料和化学产品。沸石催化剂是甲烷改质的一条潜在途径。 这项研究将集中在设计新的沸石催化剂与改进的能力，利用实验方法和理论工具。 拟议的工作汇集了沸石合成和表征，动力学研究和密度泛函理论计算的专业知识，以设计具有提高的产品收率和耐久性的金属交换沸石，用于通过两个过程进行非氧化甲烷升级：非氧化偶联和脱氢芳构化。为此，工作将集中在4个具体目标有关的刘易斯酸性（与不同的交换金属），限制效应，选择沸石框架，和理论指导的筛选协议的混合金属沸石。考虑到反应的复杂性和沸石结构内的反应环境，合成、表征和理论之间的联系对于在基于沸石的甲烷升级中取得显著进展是特别需要的。大量页岩气的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，产生大量二氧化碳--这是温室气体清单的主要贡献者。迫切需要将甲烷转化为更高价值的液体燃料和化学产品的直接方法。然而，催化剂的挑战是艰巨的。这一建议将解决目前的技术差距，并将提供一个理论基础，在该领域的沸石基甲烷转化工艺的未来研究。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，以及沸石基催化剂克服这些挑战的潜在效用。PI还将为各级学生开展教育和推广计划，以提高人们对STEM学科在解决能源相关问题方面的作用的认识。

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.