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

该项目属于EPSRC“制造未来”的研究主题，重点是催化。进行化学过程，如制造塑料和提炼燃料，需要大量的能源。催化剂减少了这种能量需求，并且在某些情况下，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。这些材料不仅价格昂贵，而且对人类和环境都有毒性。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，从元素周期表的p块进行催化。为了摆脱传统的金属基催化剂系统，我将使用笨重的刘易斯酸和碱系统来进行金属无催化。路易斯碱是具有孤对电子的化合物，而路易斯酸是接受孤对电子的化合物。当路易斯酸和路易斯碱结合时，通常由路易斯碱上的孤对提供给路易斯酸形成加合物。然而，在一个受挫的路易斯对（FLP）中，庞大的路易斯酸和碱阻止了加合物的形成，从而导致一个系统可以像传统的金属催化剂一样给予和接受电子。FLPs已被证明是活性氢化催化剂，这是一个将氢原子添加到化合物中的过程。由于活性低于目前的金属基系统，并且与工业化学缺乏兼容性，这些系统在工业中没有广泛应用。这个项目的目的是开发一个FLP系统，该系统可以兼容并提供与当前工业过程相媲美的活动。目前该领域的大部分工作都是在溶液中完成的，反应物、生成物和催化剂都溶解在溶液中，因此处于同一相。这被描述为一个同质系统；然而，我的研究的独特之处在于多相反应性。这意味着使用固体催化剂的反应物和产物，要么在气相或溶液。存在于不同相的催化剂允许试剂在催化剂上流动时具有连续的反应性，而不必分批地工作。这使得批次之间没有停机时间，提高了工艺效率。此外，不需要对催化剂、反应物和产物进行额外的分离。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，我将采用韦勒教授等人使用的固态分子有机金属（SMOM）方法，使用BArF阴离子（一种体积较大的带负电荷的离子）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。

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.