Combining Frustrated Lewis Pair (FLP) and Solid State Molecular Organometallic (SMOM) Catalysis

结合受阻路易斯对 (FLP) 和固态分子有机金属 (SMOM) 催化

• 批准号: 2329320
• 金额: --
• 依托单位: University of Oxford
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2019
• 资助国家: 英国
• 起止时间: 2019 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2329320
• 关键词: Combining; Frustrated; Lewis; Pair; FLP

This project falls within the EPSRC "Manufacturing the future" research theme, with a focus on catalysis.Performing chemical processes, such as making plastics and refining fuels, takes a great deal of energy. Catalysts reduce this energy requirement and, in some cases, allow these processes to happen at all. Current catalyst technology is based on precious metals, such as platinum and palladium. These are not only expensive but display toxicity towards humans and the environment. When designing future catalysts we must move away from the expensive and toxic precious metals and move towards more sustainable elements. My work focuses on using non-metals, such as phosphorus and boron, from the p block of the periodic table to perform catalysis. In order to move away from traditional metal-based catalyst systems I will use bulky Lewis acid and base systems to perform metal free catalysis. Lewis bases are compounds with a lone pair of electrons and Lewis acids are compounds that accept a lone pair of electrons. When a Lewis acid and base are brought together an adduct normally is formed from the lone pair on the Lewis base being donated to the Lewis acid. However, in a frustrated Lewis pair (FLP), bulky Lewis acids and bases prevent adduct formation leading to a system which can donate and accept electrons much like traditional metal catalysts. FLPs have been shown to be active hydrogenation catalysts, which is the process in which hydrogen atoms are added to a compound. These systems are not used widely in industry due to lower activity than the current metal-based systems and lack of compatibility with industrial chemistry. The purpose of this project is to develop a FLP system that may be compatible with, and, provide activities that rival the current industrial processes.Much of the current work in this field is done in solution with reactants, products and catalyst all being dissolved in solution and thus being in the same phase. This is described as a homogenous system; however, the unique aspect of my research is heterogenous reactivity. This means using a solid catalyst with reactants and products that are either in the gas or solution phase. The catalyst existing in a different phase allows for continuous reactivity as reagents flow across the catalyst, rather than having to work in batches. This allows for no down time between batches, increasing the efficiency of the process. Further to this, no additional separation of the catalyst, reactants and products is required. These factors together save on cost and energy, with benefits to both the consumer and the environment. In order to achieve heterogenous catalytic activity I will be employing the solid-state molecular organometallic (SMOM) approach used by Prof. Weller et al. using a BArF anion, a bulky negatively charged ion, to facilitate reactivity of the FLP as a single crystal. Through my project I will be collaborating with Prof Weller at the University of York.

该项目福尔斯属于EPSRC“制造未来”的研究主题，重点是催化。执行化学过程，如制造塑料和精炼燃料，需要大量的能源。催化剂降低了这种能量需求，在某些情况下，允许这些过程发生。目前的催化剂技术是基于贵金属，如铂和钯。这些不仅昂贵，而且对人类和环境具有毒性。在设计未来的催化剂时，我们必须远离昂贵和有毒的贵金属，转向更可持续的元素。我的工作重点是使用非金属，如磷和硼，从周期表的p区执行催化。为了摆脱传统的金属基催化剂体系，我将使用大体积的刘易斯酸和碱体系来进行无金属催化。刘易斯碱是具有孤对电子的化合物，而刘易斯酸是接受孤对电子的化合物。当刘易斯酸和碱结合在一起时，加合物通常由刘易斯碱上的孤对电子提供给刘易斯酸而形成。然而，在受抑的刘易斯对（FLP）中，庞大的刘易斯酸和碱阻止加合物的形成，导致可以像传统的金属催化剂那样提供和接受电子的系统。FLP已被证明是活性氢化催化剂，这是氢原子被添加到化合物中的过程。这些体系由于活性低于目前的金属基体系并且缺乏与工业化学的相容性而没有在工业中广泛使用。该项目的目的是开发一种FLP系统，该系统可以与当前的工业过程兼容，并提供与当前的工业过程相竞争的活动。目前在该领域的大部分工作都是在溶液中进行的，反应物、产物和催化剂都溶解在溶液中，因此处于同一相。这被描述为一个均匀的系统，然而，我的研究的独特之处是异质反应。这意味着使用固体催化剂，反应物和产物处于气相或溶液相。存在于不同相中的催化剂允许当试剂流过催化剂时的连续反应性，而不是必须分批工作。这使得批次之间没有停机时间，从而提高了工艺效率。此外，不需要额外分离催化剂、反应物和产物。这些因素共同节省了成本和能源，对消费者和环境都有好处。为了实现多相催化活性，我将采用Weller教授等人使用的固态分子有机金属（SrF）方法，使用BArF阴离子（一种大体积带负电荷的离子）来促进FLP作为单晶的反应性。通过我的项目，我将与约克大学的韦勒教授合作。