Atomic Efficient Catalytic Technology for Sustainable Chemical and Fuel Syntheses Enabled by Active Site Coupling and Kinetic Property Tuning

从可再生原料中高效合成能源载体和商品、特种和医药化学品是本世纪最大的挑战之一，为可持续发展的未来铺平了道路。所提出的研究计划将通过设计催化位点和反应环境来发展合成所需的基本催化知识，进而调整速率和选择性，以达到人们所追求的原子效率。具体的研究主题是轻烷烃的转化，醛/酮的选择性加氢，以及来自替代原料（页岩气，沼气和木质纤维素生物质）的轻氧化合物的偶联。该计划将采用高度集成的多学科方法，结合先进的光谱和微观技术，密度泛函数理论，以及动力学和同位素瞬态方法，在分子尺度上解开催化事件。特别关注的是活性位点在与复杂溶剂混合物接触时的结构动力学，以及在工业相关条件下催化过程中活性结构的瞬时形成。我们之前的工作已经建立了明确定义的金属和Brønsted酸位点的动力学函数以及这些反应的催化要求，具有很大的分子细节。我们还确定了关键的动力学描述符，即可测量的热力学性质，它决定了反应物在催化逗留期间的命运。在下一阶段，我们将利用机理知识和催化要求，设计具有多种类型单功能位点的复杂、分层催化剂结构，将它们包含在受限结构中，并通过聚集的溶剂分子改变它们的反应环境，以实现原子高效催化。这种策略改变了中间体的化学特性和反应性，进而决定了最终的产率。结合到这个项目是一个全面的专业发展计划，强调化学工程，化学，材料科学的多样化，跨学科的培训，以及批判性思维和领导能力。在加拿大和美国，通过强大的协同合作努力和使用世界一流的基础设施，该项目培养的高素质人才将获得强大的技术和专业技能，具有广泛的工业和全球视野。这些人员将研究可直接转移到工业催化方面的基本问题，因此加拿大能源和化学工业非常需要这些人员。

Efficient synthesis of energy carriers and commodity, specialty, and pharmaceutical chemicals from renewable feedstocks is one of the greatest challenges of this century, paving the path towards a sustainable future. The proposed research program will develop fundamental catalytic knowledge required for this synthesis via the design of catalytic sites and reaction environments and, in turn, tuning of rates and selectivities in order to attain the much sought after atomistic efficiencies. The specific research themes are the conversion of light alkanes, selective hydrogenation of aldehydes/ketones, and coupling of light oxygenates from alternative feedstocks (shale gas, biogas, and lignocellulosic biomass). The program will adapt a highly integrated, multidisciplinary approach, combining advanced spectroscopic and microscopic techniques, density functional theory, together with kinetic and isotopic transient methods, to unravel the catalytic events at the molecular scale. Specific focus is on the structural dynamics of active sites upon their contact with complex solvent mixtures and the instantaneous formation of active structures during catalysis under industrially relevant conditions. Our previous work has established the kinetic functions of well-defined metal and Brønsted acid sites and the catalytic requirements for these reactions with great molecular details. We have also identified key kinetic descriptors, i.e., measurable thermodynamic properties, that dictate the fate of the reactants during their catalytic sojourns. In this next phase, we will exploit the mechanistic knowledge and catalytic requirements, in designing complex, hierarchical catalyst structures with multiple types of mono-functional sites, containing them in confined structures and altering their reaction environment with aggregated solvent molecules for atomic efficient catalysis. Such strategies alter the chemical identity and reactivity of the intermediates and, in turn, dictate the ultimate yields. Incorporating into this program is a comprehensive professional development plan, placing strong emphasis on diverse, interdisciplinary trainings across chemical engineering, chemistry, materials science, as well as on critical thinking and leadership competency. The highly qualified personnel trained from this program will acquire strong technical and professional skill sets with broad industrial and global perspective, through strong, synergistic collaborative efforts and the use of world class infrastructure, within Canada as well as in the US. The personnel will work on fundamental problems, directly transferrable to those in industrial catalysis, as such they are much needed in the Canadian energy and chemical industries.