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 -Hartmanscience and Engineering Innovations在过去十年中，可以维持美国的能源，材料，商品，药品和精细化学品处理基础设施，使国内天然气资源能够维持国内天然气资源。天然气，水科学及其共生是可持续性的关键，在中等温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。水和甲烷的物理和化学（即天然气的最大组成部分）与大气和行星科学具有相关性。从深海到极地冰区域下方，大量天然气被捕获在世界各地的结晶水中。天然气在有机合成中的使用是值得的，但挑战在于，甲烷在中等温度下的碳 - 氢键激活及其通过碳 - 碳交叉偶联与芳基杂原子的功能化。该项目涉及五个科学的协同作用：1）CH4水合/等离子体，2）环糊精（CD）催化，3）钯催化的C-H激活/C-C交叉耦合，4）微反应工程和5）5）多层小体和在线分析。如果成功，这项研究可以将精细化学物质和药品的芳基杂原子PD催化甲基化的当前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天然气技术，但它们还将推进化学工程教育。 该项目将实现两个K-12的教育目标，除了影响PI所教导的本科和研究生级化学反应工程课程外：1）激发科学和数学学生从事化学工程领域的职业，以及2）创新方法，使学生参与化学工程研究。 PI已经与阿拉巴马州伯明翰的阿拉巴马州美术学院建立了合作伙伴关系，他在完成研究论文的第二年指导了K-12大四学生。创造的知识将通过科学和他们产生的视觉艺术中的艺术作品传播。参加阿拉巴马州美术学院的学生通常是在视觉艺术中有才华的，因此，PI建议的每个学生都会通过在伯明翰艺术漫步，阿拉巴马美术学院的巡回演出以及Pi的实验室网站上的艺术品发布来表达他们所学到的化学工程知识。预计结果将是创新，可以发现水性系统中天然气科学，K-12教育成分，它在校园寄宿生中广泛宣传，并最终在社会的广泛横截面中发展天然气的发展。crodextrins。 CH4在液态水中并用分子扩散催化CH4水合物形成通常可以控制这两个过程。通过包含化合物的微反应工程获得的分子水平理解及其在C-H活化/C-C交叉偶联中的复合物可以提高天然气作为多相有机合成的经济原料的多功能性。 i）通过在线分析通过​​在线分析进行创新的微型系统来了解理解，以连续多相C-C交叉耦合CH4，ii）发现在有机 - 液体水接口上使用Alpha-cta-cta，beta-ct的PD催化的CH4的PD催化的CH4的C-C交叉偶联CH4，芳基杂原子偶联离子化CH4与芳基杂原子在冷等离子体液接口处的交叉偶联，并阐明控制C-C交叉偶联的催化循环。该项目将PI在他的博士研究中研究无机纳入化合物的经验，创新的科学和技术使美国能够在他的研究生生涯中获得天然气，研究有机合成的微化学系统，以在其后可关注的研究中研究其学术研究，并在他的学术实验室中构建了甲基甲烷甲烷的学术综合综合综合综合体和水水合性的实验室。