UNS:Catalysis at Acid-Base Site Pairs: Thermodynamic and Kinetic Studies of Aldol Additions to Upgrade Biofuels on Metal and Mixed Metal Oxides

未来几十年，全球能源消耗将急剧增加，从而刺激了对生物质等可再生能源生产的燃料和化学品的需求。虽然将生物质转化为诸如乙醇之类的化学物质的过程是众所周知的，但将这些发酵产物进一步加工成构成燃料和化学物质的大分子目前效率低下，而且还没有得到很好的理解。该项目将研究专门设计的催化材料的新组合，以促进发酵产物耦合成柴油燃料、润滑剂和化学原料。通过了解详细的催化化学及其与催化材料结构和组成的关系，该研究将为新型催化剂材料奠定基础，这些催化剂材料可以比现有工艺更有效地将发酵产物转化为更高价值的产品，并显著节省能源。这项工作还将为培训科学、技术和工程方面的研究生和本科生提供机会，特别强调为女学生提供机会。大多数生物质升级过程依赖于酸性催化剂。碱性催化剂通常避免使用，因为在发酵过程中会受到水和二氧化碳的毒害。这些研究人员已经认识到有机会将酸性和碱性催化功能结合到一个催化剂中，以一种促进醛醇型缩合（即链式生长）反应的方式，而不会产生通常的中毒效应。他们将通过研究超过25种技术上相关的催化剂来实现这一目标，这些催化剂含有一系列酸位、碱位和酸碱位对。使用实验工具的组合，他们将表征酸、碱和酸碱对位点的数量和强度，然后将这些位点上的醇和醛吸附与详细的醛缩合动力学和关键过渡态的识别联系起来。这项工作的更广泛的科学影响将是为设计更活跃和稳定的催化剂以生产碳中性生物燃料和化学品提供指导原则。此外，首席研究员正在建立一个本科生研究项目，重点是培养研究生女性导师，与STEM领域的本科生学员一起工作。

Flaherty, 1511819Global energy consumption will increase dramatically in the next several decades, thus stimulating demand for fuels and chemicals produced from renewable sources such as biomass. While the processes for converting biomass to chemicals such as ethanol are well-known, the further processing of those fermentation products to the larger molecules that make up fuels and chemicals is presently inefficient and not well understood. This project will investigate new combinations of catalytic materials specifically designed to promote the coupling of fermentation products into diesel fuel, lubricants and chemical feedstocks. By understanding the detailed catalytic chemistry and its relationship to the structure and composition of the catalytic materials, the research will lay the groundwork for a new class of catalyst materials that can convert fermentation products into higher-value products both more efficiently and with significant energy savings compared to existing processes. The work will also provide opportunities for the training of both graduate students and undergraduates in science, technology, and engineering, with special emphasis on providing opportunities to female students.Most biomass upgrading processes rely on acidic catalysts. Basic catalysts have generally been avoided because of poisoning by water and carbon dioxide associated with fermentation processes. These researchers have recognized an opportunity to combine both acidic and basic catalytic functions into a single catalyst in a way that promotes aldol type condensation (i.e. chain growth) reactions without the usual poisoning effects. They will do this by investigating more than 25 technologically relevant catalysts containing a range of acid sites, base sites, and acid-base site pairs. Using a combination of experimental tools, they will characterize the number and strength of acid, base, and acid-base pair sites and then relate alcohol and aldehyde adsorption on those sites to detailed aldol condensation kinetics and identification of critical transition states. The broader scientific impact of this work will be to produce guiding principles for the design of more active and stable catalysts for the production of carbon-neutral biofuels and chemicals. In addition, the principal investigator is building an undergraduate research program that focuses on developing graduate-student female mentors to work with undergraduate mentees in the STEM areas.