CAS: Collaborative Research: Separating Electronic and Geometric Effects in Compound Catalysts: Examining Unique Selectivities for Hydrogenolysis on Transition Metal Phosphides

将生物质、页岩和石油原料转化为增值燃料和化学品需要昂贵的稀有金属催化剂来加速化学反应。对材料化学家和工程师来说，这种更便宜、更富土的催化剂的设计是一个重大挑战。将廉价元素与稀有金属结合可以在保持或提高催化剂性能的同时降低成本。以前，由于不了解这些催化剂的结构和组成对性能和稳定性的依赖性，这种策略受到限制。在这个项目中，Hibbitts博士（佛罗里达大学）、Flaherty博士（伊利诺伊大学厄巴纳-香槟分校）和Plaisance博士（路易斯安那州立大学）正在合作了解金属催化剂的基本行为，最初的重点是金属磷化材料。这种理解将指导未来催化剂的设计，为化学工业提供有针对性的反应速率和选择性的改进。Drs。hibitts， Flaherty和Plaisance参加了激发和激励学生学习STEM主题的外展活动。夏季实习、师徒关系和互动研讨会只是这些教师在各自机构中使用的一些活动，以增加未来化学劳动力的规模和多样性。化学系化学催化项目的资助使Hibbitts博士（佛罗里达大学）、Flaherty博士（伊利诺伊大学厄巴纳-香槟分校）和Plaisance博士（路易斯安那州立大学）之间的多研究员合作成为可能。这些研究人员将对过渡金属磷化物中p原子的电子和几何效应如何导致生物质衍生氧合物中C-O键的区域选择性断裂有一个基本的理解。过渡金属磷化物是稳定、廉价、高效的加氢脱氧催化剂，因为它们选择性地切割难以被其他金属催化剂激活的位阻C-O键。这些C-O断裂途径从生物质分子中产生增值化学物质。对这类材料和指导结构-功能关系的广泛理解目前还不存在，但将在本项目中解决。在可能的情况下，这些材料的合成和表征将验证密度泛函理论（DFT）的预测和模型。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

The conversion of biomass, shale, and petroleum feedstocks into value-added fuels and chemicals requires costly and rare metal catalysts to speed up the chemical reactions. This design of less expensive and more earth abundant catalysts is a major challenge to materials chemists and engineers. Combining inexpensive elements with rare metals can reduce costs while maintaining or improving catalyst performance. Previously, this strategy has been limited because the dependence of the performance and stability on the structure and composition of these catalysts was not understood. In this project, Dr. Hibbitts (University of Florida), Dr. Flaherty (University of Illinois – Urbana-Champaign), and Dr. Plaisance (Louisiana State University) are collaborating to understand the fundamental behavior of metal catalysts with an initial focus on metal phosphide materials. This understanding will guide the design of future catalysts that provide targeted improvements in reaction rates and selectivities of interest to the chemical industry. Drs. Hibbitts, Flaherty, and Plaisance participate in outreach activities that excite and motivate students into studying topics within STEM. Summer internships, mentor-mentee formations, and interactive workshops are just some of the activities these faculty use at their respective institutions to increase the size and diversity of the future chemistry workforce.Funding from the Chemical Catalysis Program of the Division of Chemistry is enabling a multi-investigator collaboration among Dr. Hibbitts (University of Florida), Dr. Flaherty (University of Illinois – Urbana-Champaign), and Dr. Plaisance (Louisiana State University). These researchers will develop a fundamental understanding of how the electronic and geometric effects of P-atoms in transition metal phosphides lead to regioselective rupture of C–O bonds in biomass-derived oxygenates. Transition metal phosphides are stable, inexpensive, and productive catalysts for hydrodeoxygenation because they selectively cleave sterically-hindered C–O bonds that are difficult to activate with other metal catalysts. These C–O rupture pathways produce value-added chemicals from biomass molecules. A broad understanding of this class of materials and guiding structure-function relationships do not currently exist but will be addressed in this project. Where possible, synthesis and characterization of these materials will validate density functional theory (DFT) predictions and models.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.