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: 1954426
• 负责人: David Hibbitts
• 金额: $ 23.61万
• 依托单位: University of Florida
• 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=1954426&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.

生物质，页岩和石油原料转化为增值燃料和化学物质需要昂贵且稀有的金属催化剂，以加快化学反应的速度。这种较便宜和更富土的催化剂的设计是化学家和工程师的主要挑战。将廉价的元素与稀有金属相结合可以降低成本，同时保持或改善催化剂性能。以前，由于不了解性能和稳定性对这些催化剂的结构和组成的依赖性。在该项目中，希比茨博士（佛罗里达大学），伊利诺伊大学 - 乌尔巴纳·坎佩恩大学）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，最初侧重于金属磷化物材料。这种理解将指导未来催化剂的设计，这些催化剂可为化学工业提供针对性的改善反应速率和感兴趣的选择性。博士。 Hibbitts，Flaherty和对宣传活动的参与，激发了学生在STEM内学习主题。 Summer interships, mental-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 Plaisance博士（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-原子的电子和几何影响如何导致C – O键在生物质衍生的氧化酸盐中的调节性破裂。过渡金属磷化物是稳定，廉价的和产物催化剂的加氢氧合，因为它们有选择地清除了在其他金属催化剂中难以激活的空间障碍的C – O键。这些C – O破裂途径从生物质分子中产生增值化学物质。目前不存在对这类材料和指导结构功能关系的广泛理解，但将在该项目中解决。在可能的情况下，这些材料的综合和表征将验证密度功能理论（DFT）预测和模型。该奖项反映了NSF的法定任务，并使用基金会的知识分子优点和更广泛的影响来审查标准，通过评估被认为是宝贵的支持。

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
• 期刊: Journal of Catalysis
• 影响因子: 7.3
• 作者: Waldt, Conor;Montalvo-Castro, Hansel;Almithn, Abdulrahman;Loaiza-Orduz, Álvaro;Plaisance, Craig;Hibbitts, David
• 通讯作者: Hibbitts, David