CAREER: Palladium-Catalyzed C-H Activation/C-C Cross-Coupling of CH4 Hydrates and Plasma using Cyclodextrin Ligand in Multiphase Microsystems

1453062-哈特曼过去十年的科学和工程创新使国内天然气资源能够支撑美国的S能源、材料、大宗商品、制药和精细化学品加工基础设施。天然气、水科学及其共生是可持续发展的关键，在中等温度(200摄氏度)下使用天然气进行有机合成的新的、经济的方法仍然是一个挑战。水和甲烷(即天然气的最大组成部分)的物理和化学在大气和行星科学中具有相关性。从深海海底到极地冰层之下，世界各地都有大量的天然气被困在结晶水中。天然气在有机合成中的应用有其优点，但挑战在于在中等温度下可控地激活甲烷的碳氢键，并通过碳-碳与芳基杂原子的交叉偶联来实现它们的功能化。该项目涉及五个科学的协同作用：1)甲烷水合物/等离子体，2)环糊精(CD)催化，3)钯催化的C-H活化/C-C交叉偶联，4)微反应工程，5)多相微流控在线分析。如果这项研究成功，这项研究可以将目前用于精细化学品和药物的钯催化芳基杂原子甲基化的合成方法的成本降低至少一个数量级。由此产生的科学发现将广泛影响水性天然气技术，但它们也将促进化学工程教育。该项目将实现两个K-12教育目标，而不是影响PI教授的本科生和研究生水平的化学反应工程课程：1)激励科学和数学学生追求化学工程职业，2)创新方法，让学生远程参与化学工程研究。PI已经与阿拉巴马州伯明翰的阿拉巴马美术学院建立了合作伙伴关系，在那里他正在指导一名K-12高年级学生完成他的研究论文，这是他第二年的工作。创造的知识将通过艺术作品在其产生的科学和视觉艺术中传播。在阿拉巴马州美术学院注册的学生通常在视觉艺术方面有天赋，因此PI建议的每个学生都将通过参观伯明翰艺术步行街、阿拉巴马州美术学院的展览和在PI的实验室网站上发布艺术照片来表达他们所学到的化学工程知识。预计结果将是创新，发现水体系中的天然气科学，这是K-12教育的一个组成部分，广泛延伸到校园边界之外，并最终促进天然气在社会广泛领域的利用。环糊精(α-、β-和伽马-CD)是天然存在的和合成的有机包合物，已知可以稳定液态水中的CH4，并催化CH4水合物的形成，分子扩散通常控制这两个过程。通过对包合物及其络合物在C-H活化/C-C交叉偶联中的微反应工程所获得的分子水平的了解，可以提高天然气作为多相有机合成的经济原料的通用性。这方面的理解将从以下方面了解到：一)创新具有在线分析的微系统，用于甲烷的连续多相C-C交叉偶联；二)发现钯催化的储存在水合物中的甲烷与有机-液态水界面的芳基杂原子之间的C-C交叉偶联；三)发现钯催化的电离甲烷与冷等离子体-液水界面的芳基杂原子的C-C交叉偶联；以及四)阐明控制C-C交叉偶联的催化循环(S)。该项目将派在博士研究中研究无机包合物的十年经验结合在一起，在他的研究生生涯中创新使美国能够确保天然气安全的科学技术，在他的博士后研究中研究用于有机合成的微型化学系统，并利用在天然气水合物和亲水性有机合成方面的发现建立他的水甲烷转化学术实验室。

1453062 - HartmanScience and engineering innovations over the last decade have enabled domestic natural gas resources that could sustain the U.S.'s energy, materials, commodity, pharmaceutical, and fine chemicals processing infrastructure. Natural gas, water science, and their symbiosis are keys to sustainability, and novel, economical approaches to the use of natural gas in organic synthesis at moderate temperatures (200 degC) remains a challenge. The physics and the chemistry of water and methane (i.e., the largest component fraction of natural gas) have relevance in the atmospheric and planetary sciences. Massive quantities of natural gas are entrapped in crystalline water throughout the world, from the deep seabed to beneath the polar ice regions. Natural gas has merit for its use in organic synthesis but the challenges are in the controlled activation of carbon-hydrogen bonds of methane at moderate temperatures and their functionalization via carbon-carbon cross-coupling with aryl heteroatoms. This project involves the synergy of the five sciences: 1) CH4 hydrates/plasma, 2) cyclodextrin (CD) catalysis, 3) palladium-catalyzed C-H activation/C-C crosscoupling,4) microreaction engineering, and 5) multiphase microfluidics with online analytics. If successful, this research could reduce the cost of current synthetic methodologies of Pd-catalyzed methylations of aryl heteroatoms for fine chemicals and pharmaceuticals by at least an order of magnitude. The resulting scientific discoveries will broadly impact aqueous natural gas technology, but they will also advance chemical engineering education. The project will accomplish two K-12 educational goals beyond affecting the undergraduate and the graduate-level chemical reaction engineering curricula that the PI teaches: 1) inspire science and mathematics students to pursue careers in chemical engineering, and 2) innovate approaches to remotely involve students with chemical engineering research. The PI has already established a partnership with the Alabama School of Fine Arts, Birmingham, AL where he is mentoring a K-12 senior for the second year towards the completion of his research thesis. The knowledge created will be disseminated through works of art in both the science and the visual arts they generate. Students enrolled in the Alabama School of Fine Arts are commonly gifted in the visual arts, and thus each student the PI advises will express the chemical engineering knowledge they learn by touring exhibitions at the Birmingham Art Walk, the Alabama School of Fine Arts, and the posting of artwork photographs on the PI's laboratory website. The outcomes are anticipated to be innovations that discover the science of natural gas in aqueous systems, a K-12 educational component that broadly outreaches beyond the campus boarders, and ultimately the advancement of natural gas utilization in a broad cross-section of society.Cyclodextrins (alpha-, beta-, and gamma-CD's), both naturally occurring and synthetically prepared organic inclusion compounds, are known to stabilize CH4 in liquid water and to catalyzed CH4 hydrate formation with molecular diffusion often controlling both processes. Molecular-level understanding acquired via the microreaction engineering of inclusion compounds and their complexes in C-H activation/C-C cross-coupling could advance the versatility of natural gas as an economical feedstock for multiphase organic synthesis. The understanding will be learned by i) innovating microsystems with online analytics for continuous multiphase C-C cross-couplings of CH4, ii) discovering the Pd-catalyzed C-C cross-coupling of CH4 stored in hydrates with aryl heteroatoms at organic-liquid water interfaces using alpha-, beta-, and gamma-CD's, iii) discovering the Pd-catalyzed C-C cross-coupling of ionized CH4 with aryl heteroatoms at cold plasma-liquid water interfaces, and iv) elucidating the catalytic cycle(s) that control the C-C cross-couplings. The project couples the PI's decade of experiences studying inorganic inclusion compounds in his doctoral research, innovating science and technology that are enabling the US to secure natural gas in his post-graduate career, researching microchemical systems for organic synthesis in his postdoctoral research, and building his academic laboratory on aqueous methane conversion with discoveries on gas hydrates and hydrophilic organic synthesis.