Catalytic transformations of oxygen- and nitrogen-containing substrates

含氧和含氮底物的催化转化

• 批准号: RGPIN-2014-05844
• 负责人: Kerton, Francesca
• 金额: $ 3.13万
• 依托单位: Memorial University of Newfoundland
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2015
• 资助国家: 加拿大
• 起止时间: 2015-01-01 至 2016-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=588653
• 关键词: Catalytic; transformations; oxygen; nitrogen; containing

During the next 5 years, the Kerton group will develop new ways to make small organic molecules and plastics using renewable feedstocks alone or in combination with oil-based chemicals. Most renewables (carbon dioxide, sugars, amino acids and related naturally-sourced molecules) contain oxygen and/or nitrogen heteroatoms. This contrasts with chemicals obtained from gas, oil or coal that typically contain very few non-carbon or -hydrogen atoms. Therefore, new chemical methods are needed, because during the past century, “the petroleum age”, chemists have focused their efforts on selective conversion of hydrocarbons into desirable products. Due to depleting fossil fuel reserves, chemists must now strive to selectively convert renewable feedstocks into higher value products. This means that new reactions and new catalysts need to be developed. Furthermore, utilization of carbon dioxide as a starting material for new products is a crucial field of research for timely reductions in our carbon footprint. In the Kerton group, three inter-connected streams of research are being pursued towards this goal: (1) New nitrogen-containing chemicals from biomass and their reactivity; (2) New polymers derived from renewable feedstocks; and (3) New catalytic transformations of alcohols, ethers, amines and amides. Within these streams of fundamental research, several projects target global areas of importance highlighted by governments and research organizations (e.g. ACS Green Chemistry Institute Roundtables, and NSERC strategic areas such as Sustainable Manufacturing): carbon dioxide activation and utilization, catalytic oxidation reactions, and new nitrogen-centered chemistry. Advances in these areas could have a significant impact on Canada’s economy and environment in the next 15-30 years. Few researchers in the field of renewable chemicals are targeting both small molecule and polymer targets, therefore, due to this two-pronged combined approach, new and important discoveries will be made. For example, a new molecular building block, which we have prepared from waste shrimp shells, could lead to the production of a renewable polymer with properties similar to Kevlar (found in bullet-proof vests). Molecules, materials and methods discovered as part of this research program may find utility in the total synthesis of bioactive compounds (medicine), in the production of high-value engineering materials or commodity plastics (chemical manufacturing), or as a stepping-stone for future research and discoveries (knowledge base). Also, a large number of both undergraduate and graduate students (HQP) will be trained and they will add to the strength of Canada’s workforce in technological fields aimed at sustainable development and pollution reduction. Kerton group HQP are encouraged to follow the principles of green chemistry and engineering, whilst obtaining training in fundamental chemistry problem solving and expertise. We are interested in mechanism-driven research in that HQP are asked to obtain kinetic and thermodynamic data for the chemical processes that they discover and study. Once such data is obtained, we strive to use this information to improve on initial discoveries in subsequent investigations. Where possible, in situ FT-IR and NMR spectroscopic measurements are performed under ‘real’ reaction conditions e.g. HQP will make use of our modified pressure vessel and ReactIR system to study activation of carbon dioxide. New discoveries that are made as part of this research program will ultimately lead to economic and environmental benefits for Canada and Canadians.

在接下来的5年里，Kerton集团将开发新的方法，单独使用可再生原料或与油基化学品结合使用来制造有机小分子和塑料。大多数可再生能源（二氧化碳，糖，氨基酸和相关的天然来源的分子）含有氧和/或氮杂原子。这与从天然气、石油或煤中获得的化学品形成对比，这些化学品通常含有非常少的非碳或氢原子。因此，需要新的化学方法，因为在过去的世纪“石油时代”，化学家们将精力集中在将碳氢化合物选择性转化为所需产品上。由于化石燃料储量的枯竭，化学家现在必须努力将可再生原料选择性地转化为更高价值的产品。 这意味着需要开发新的反应和新的催化剂。此外，利用二氧化碳作为新产品的原材料是及时减少碳足迹的关键研究领域。在Kerton集团中，三个相互关联的研究流正在朝着这一目标努力：（1）来自生物质的新含氮化学品及其反应性;（2）来自可再生原料的新聚合物;（3）醇，醚，胺和酰胺的新催化转化。在这些基础研究中，有几个项目针对政府和研究组织（例如ACS绿色化学研究所圆桌会议和NSERC战略领域，如可持续制造）强调的全球重要领域：二氧化碳活化和利用，催化氧化反应和新的氮为中心的化学。这些领域的进展可能在未来15-30年内对加拿大的经济和环境产生重大影响。在可再生化学品领域，很少有研究人员同时针对小分子和聚合物目标，因此，由于这种双管齐下的方法，将有新的重要发现。例如，我们从废弃的虾壳中制备的一种新的分子构建块，可以导致生产一种可再生聚合物，其特性类似于Kevlar（在防弹背心中发现）。作为该研究计划的一部分发现的分子，材料和方法可能在生物活性化合物的全合成（医学），高价值工程材料或商品塑料的生产（化学制造）中找到实用性，或作为未来研究和发现的垫脚石（知识库）。 此外，大量的本科生和研究生将接受培训，他们将增加加拿大在可持续发展和减少污染的技术领域的劳动力。鼓励Kerton集团的HQP遵循绿色化学和工程的原则，同时获得基础化学问题解决和专业知识的培训。 我们对机制驱动的研究感兴趣，因为HQP被要求获得他们发现和研究的化学过程的动力学和热力学数据。一旦获得这些数据，我们将努力利用这些信息来改进后续调查中的初步发现。在可能的情况下，在“真实的”反应条件下进行原位FT-IR和NMR光谱测量，例如HQP将利用我们改进的压力容器和ReactIR系统来研究二氧化碳的活化。作为这项研究计划的一部分，新发现最终将为加拿大和加拿大人带来经济和环境效益。