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，全球能源消耗将大幅增加，从而刺激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乙醇等化学品的过程众所周知，但将这些发酵产物进一步加工成组成燃料和化学品的更大分子目前效率低下，也没有得到很好的了解。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、润滑油和化学原料。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，这项研究将为新型催化材料奠定基础，与现有工艺相比，这种材料可以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。这项工作还将为研究生和本科生提供科学、技术和工程方面的培训机会，特别是为女学生提供机会。大多数生物质升级过程依赖酸性催化剂。由于与发酵过程相关的水和二氧化碳中毒，基本催化剂通常被避免。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，以一种方式促进羟醛缩合(即链生长)反应，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做到这一点，这些催化剂包含一系列的酸中心、碱中心和酸碱中心对。使用一系列实验工具，他们将表征酸、碱和酸碱对位置的数量和强度，然后将乙醇和醛在这些位置上的吸附与详细的羟醛缩合动力学和临界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更稳定的催化剂以生产碳中性生物燃料和化学品制定指导原则。此外，首席研究员正在建立一个本科生研究计划，重点是培养研究生女性导师，以便在STEM领域与本科生导师合作。

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.