Collaborative Research: ECO-CBET: Methane Conversion by Merging Atmospheric Plasma with Transition-Metal Catalysis

甲烷是天然气的主要成分，是石油的一种丰富的替代化学原料。甲烷也是一种强有力的温室气体，因此油田中多余的天然气被燃烧，以避免向大气中释放甲烷。将天然气和过剩的甲烷转化为液体燃料和化学品将是利用自然资源和减少温室气体排放的有效方式。然而，当使用传统的热工艺时，这种转换是具有挑战性的。低温等离子体反应堆技术是天然气甲烷转化为燃料和化学品的诱人工具，因为它能够在比热过程低得多的温度下激活碳氢化合物。这不仅带来了提高费率的潜力，还为更理想的产品选择性打开了大门。尽管这项技术很有吸引力，但其实际实施一直受到该技术背后复杂的化学、物理和运输过程的阻碍。这项研究项目研究了在大气等离子体中进行的催化过程中天然气的价化。人们对等离子体中甲烷的催化转化知之甚少，因此了解这一过程可能会转化为更可持续的甲烷转化化学路线。该研究项目将与教育活动相结合，培训学生设计可持续能源的解决方案，一个没有污染和废物的未来，以及减少温室气体排放。该研究项目旨在结合两项技术，即等离子体促进的甲烷活化和过渡金属催化，以解决甲烷价态问题。大气甲烷等离子体的物理性质和化学反应性还不是很清楚，等离子体产物与过渡金属配合物的后续反应也不是很清楚。微流控技术将被用来产生性质可控的等离子体。然后，将进行实验，以探索等离子体与有机自由基受体的反应性，了解等离子体如何与有机自由基受体和有机金属络合物相互作用，并探索甲烷等离子体中碳-碳和碳-氮键的形成。最终目标是量化等离子体与有机自由基受体和过渡金属络合物的反应性，以便将甲烷转化为更大的烷烃、取代芳烃和胺化合物。规模扩大和固有能源效率对等离子体辅助化学转化过程的实施提出了潜在的挑战。这项研究将揭示新的方法，将甲烷的反应性和产品选择性提高到将基本发现转化为工业应用所需的水平。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

Methane is the primary component of natural gas and represents an abundant, alternative chemical feedstock to petroleum. Methane is also a potent greenhouse gas, so excess natural gas from oil fields is flared in order to avoid releasing methane into the atmosphere. Converting natural gas and excess methane into liquid fuels and chemicals would be an efficient way to use natural resources and reduce greenhouse gas emissions. This conversion is challenging, however, when utilizing conventional thermal processes. Low temperature plasma reactor technology is an enticing tool for natural gas methane valorization to fuels and chemicals given its capability to activate hydrocarbons at much lower temperature than thermal processes. Not only does this bring potential to improve rates, but also opens the door to more desirable product selectivity. Despite its allure, practical implementation has been impeded by the complexity of the chemical, physical, and transport processes underlying the technology. This research project studies the valorization of natural gas using catalytic processes conducted in atmospheric plasmas. Little is known about the catalytic conversion of methane in plasmas, so understanding this process could translate into more sustainable chemical routes for methane conversion. The research project will be integrated with educational activities that train students to engineer solutions for sustainable energy, a future without pollution and waste, and reducing greenhouse gas emissions.The research project aims to combine two technologies, plasma-promoted methane activation and transition-metal catalysis, to address methane valorization. The physical properties and chemical reactivity of atmospheric methane plasma are not well understood, nor are subsequent reactions of plasma products with transition metal complexes. Microfluidics techniques will be employed to generate plasmas with controllable properties. Then, experiments will be performed to probe the reactivity of plasmas with organic radical acceptors, to understand how plasmas interact with both organic radical acceptors and organometallic complexes, and to explore carbon-carbon and carbon-nitrogen bond formation in methane plasmas. The ultimate objective is to quantify the reactivity of plasmas with organic radical acceptors and transition metal complexes in order to convert methane into larger alkanes, substituted arenes, and amine compounds. Scale-up and intrinsic energy efficiency present potential challenges to the implementation of plasma-assisted chemical conversion processes. This study will uncover novel approaches for increasing methane reactivity and product selectivity to levels needed for translating fundamental findings into industrial applications.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.