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

1453062 - hartman过去十年的科学和工程创新使美国国内的天然气资源能够维持美国的经济增长中国的能源、材料、商品、医药和精细化工加工基础设施。天然气、水科学及其共生关系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颖、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）的物理和化学与大气和行星科学有关。从海底深处到极地冰区，世界各地的结晶水中蕴藏着大量的天然气。天然气在有机合成中具有一定的优势，但其难点在于如何在中等温度下控制甲烷碳氢键的活化，并通过与芳基杂原子的碳-碳交叉偶联实现甲烷的功能化。该项目涉及五个学科的协同：1)CH4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)多相微流体与在线分析。如果成功，这项研究可以将目前用于精细化学品和药物的pd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含水天然气技术，但它们也将推动化学工程教育。除了影响PI教授的本科和研究生水平的化学反应工程课程外，该项目还将实现两个K-12教育目标：1)激励科学和数学专业的学生从事化学工程方面的职业；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关系，在那里他正在指导一名K-12大四学生完成他的研究论文。所创造的知识将通过科学艺术作品和视觉艺术作品进行传播。在阿拉巴马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在伯明翰艺术步道和阿拉巴马美术学院的巡回展览来表达他们学到的化学工程知识，并在PI的实验室网站上发布艺术作品照片。预计其结果将是发现水系统中天然气科学的创新，广泛扩展到校园边界以外的K-12教育内容，并最终在广泛的社会各界中推进天然气利用。环糊精（α -、β -和γ - cd），无论是天然存在的还是合成的有机包合化合物，都具有稳定液态水中的CH4和催化CH4水合物形成的作用，而分子扩散通常控制这两个过程。通过包合物及其配合物在C-H活化/C-C交叉偶联中的微反应工程获得的分子水平的理解，可以促进天然气作为多相有机合成的经济原料的多功能性。通过i)创新微系统，对CH4的连续多相C-C交叉耦合进行在线分析，ii)使用α -， β -和γ - cd发现储存在水合物中的CH4与芳基杂原子在有机-液态水界面上的pd催化的C-C交叉偶联，iii)发现pd催化的电离CH4与芳基杂原子在冷等离子体-液态水界面上的C-C交叉偶联。iv)阐明控制C-C交叉偶联的催化循环。该项目结合了PI博士十年来研究无机包裹体化合物的经验，在研究生生涯中创新科学和技术，使美国能够获得天然气，在博士后研究中研究有机合成的微化学系统，以及在天然气水合物和亲水有机合成方面的发现建立了他的含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.