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

CAS：合作研究：分离复合催化剂中的电子效应和几何效应：检验过渡金属磷化物氢解的独特选择性

• 批准号: 1954611
• 负责人: Craig Plaisance
• 金额: $ 21.87万
• 依托单位: Louisiana State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-05-01 至 2025-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954611&HistoricalAwards=false
• 关键词: CAS; Collaborative; Research; Separating; Electronic

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.

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，这种更便宜且地球资源丰富的催化剂的设计对材料化学家和工程师来说是一个重大挑战。将廉价元素与稀有金属结合可以降低成本，同时保持或提高催化剂性能，因为在该项目中，性能和稳定性对这些催化剂的结构和组成的依赖性尚不清楚。 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物材料。这一认识将指导未来催化剂的设计，从而有针对性地提高化学工业感兴趣的反应速率和选择性。激发和激励学生学习 STEM 主题的外展活动、导师-学员培训和互动研讨会只是这些教师在各自机构开展的一些活动，旨在扩大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得 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 Dr. Flaherty 之间的多位研究者合作成为可能。 Plaisance（路易斯安那州立大学）。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的含氧化合物中 C-O 键的区域选择性断裂有一个基本的了解。廉价且高产的加氢脱氧催化剂，因为它们选择性地裂解难以用其他金属催化剂激活的空间位阻 C-O 键。目前尚不存在对此类材料和指导结构功能关系的广泛理解，但将在可能的情况下解决这些材料的合成和表征，以验证密度泛函。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Role of phosphorous in transition metal phosphides for selective hydrogenolysis of hindered C–O bonds

过渡金属磷化物中磷对受阻 C–O 键选择性氢解的作用

• DOI: 10.1016/j.jcat.2023.02.011
• 发表时间: 2023-05
• 期刊: Journal of Catalysis
• 影响因子: 7.3
• 作者: Waldt, Conor;Montalvo;Almithn, Abdulrahman;Loaiza;Plaisance, Craig;Hibbitts, David
• 通讯作者: Hibbitts, David