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

职业：在多相微系统中使用环糊精配体进行钯催化的 CH4 水合物和等离子体的 C-H 活化/C-C 交叉偶联

• 批准号: 1453062
• 负责人: Ryan Hartman
• 金额: $ 50.1万
• 依托单位: University of Alabama Tuscaloosa
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-08-15 至 2015-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1453062&HistoricalAwards=false
• 关键词: CAREER; Palladium; Catalyzed; Activation; Cross

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.

1453062 - Hartman过去十年的科学和工程创新使国内天然气资源能够维持美国的能源、材料、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）下在有机合成中使用天然气的新颖、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相关。从深海海底到极地冰区下方，全世界都有大量天然气被包裹在结晶水中。天然气在有机合成中具有优点，但挑战在于在中等温度下控制甲烷碳-氢键的活化以及通过与芳基杂原子的碳-碳交叉偶联进行官能化。该项目涉及五门科学的协同作用：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，以及 5) 具有在线分析功能的多相微流体。如果成功，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 教授的本科生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) 激励科学和数学学生追求化学工程职业，2) 远程参与的创新方法从事化学工程研究的学生。该 PI 已经与阿拉巴马州伯明翰美术学院建立了合作伙伴关系，他正在该学院第二年指导一名 K-12 高年级学生完成他的研究论文。所创造的知识将通过其产生的科学和视觉艺术艺术作品进行传播。就读于阿拉巴马美术学院的学生通常在视觉艺术方面有天赋，因此 PI 建议的每位学生都会通过参观伯明翰艺术步行街、阿拉巴马美术学院和在 PI 实验室网站上发布艺术品照片。预计成果将是发现水系统中天然气科学的创新，这是广泛延伸到校园寄宿生之外的 K-12 教育内容，并最终推动社会各阶层的天然气利用的进步。 环糊精（α-、β-和 γ-CD），天然存在的和合成制备的有机包合物，已知可以稳定液态水中的 CH4 并催化 CH4 水合物形成，分子扩散通常控制这两个过程。通过包合物及其复合物在 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) 通过在线分析创新微系统来了解 CH4 的连续多相 C-C 交叉偶联，ii) 使用 α 发现水合物中存储的 CH4 与芳基杂原子在 Pd 催化下的 C-C 交叉偶联。 -、β-和γ-CD，iii) 发现 Pd 催化的 C-C 交叉偶联iv) 阐明了控制 C-C 交叉偶联的催化循环。该项目结合了 PI 十年的经验：在他的博士研究中研究无机包合物，在他的研究生生涯中创新科学和技术，使美国能够确保天然气安全，在他的博士后研究中研究有机合成的微化学系统，并建立他的学术实验室致力于水甲烷转化，并在天然气水合物和亲水有机合成方面有所发现。