Understanding electrochemical hydrogenation reactions over post-transition metal electrodes: the role of incidental mediators and metastable phases

了解后过渡金属电极上的电化学氢化反应：偶然介体和亚稳态相的作用

• 批准号: 2301381
• 负责人: Adam Holewinski
• 金额: $ 59.94万
• 依托单位: University of Colorado at Boulder
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-08-01 至 2026-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2301381&HistoricalAwards=false
• 关键词: Understanding; electrochemical; hydrogenation; reactions; over; Understanding; electrochemical; hydrogenation; reactions; over

Electrochemistry enables the use of electrical energy to drive chemical reactions. These types of reactions are increasingly interesting due to their compatibility with renewable electricity infrastructure. The reactions occur by interaction of molecules with materials known as electrodes, which are held at an applied voltage and can exhibit catalytic properties when the molecules contact their surfaces. This project will investigate a phenomenon where the electrode material is not static, but instead generates corrosion products that mediate the catalytic reactions. In many cases, corrosion is seen as a detrimental process; however, in this project the investigators aim to use corrosion products purposefully and productively. The mechanism is not yet well understood, and gaining the ability to control and exploit it could have consequences for the design of electrochemical systems for a wide array of chemical production. Specific reactions to be studied in this project relate to the conversion of biomass-derived molecules to make green fuels and chemical precursors to biodegradable plastics. In addition to the expected benefits of Ph.D. training for workforce development, the PIs will establish research opportunities for undergraduates as well as educational materials for larger groups of students, scientists, and non-expert community members. Several of the initiatives to be supported are ongoing, while the project will add a new research experience opportunity for local community college instructors to help in shaping future curriculum and guiding students in continuing from two-year to four-year degree programs.The goal of this project is to understand the extent to which reduced metal species, generated by cathodic corrosion processes such as the formation of dissolved metal hydrides or anions, may mediate reduction of molecules. While traditionally viewed as detrimental side reactions, the project explores the hypothesis that these cathodic corrosion products can mediate homogeneous reduction, even as the primary mechanism in some cases. This hypothesis will be evaluated against possible mechanisms with heterogeneous charge transfer from either the native electrode material or from metastable in-situ phases such as solid metal hydrides or alkali alloys. Specific reactivity studies will involve reduction of levulinic acid (LA) as a testbed. This molecule is derived from renewable biomass and can be electro-reduced to several valuable products. The PIs have obtained preliminary evidence that corrosion-product mediation may be involved on materials that are highly selective to making hydroxyvaleric acid (a monomer for biodegradable plastics) and gamma-valerolactone (a green solvent and biofuel) from LA. The plan is to combine rigorous kinetic measurement tools, quantum chemical calculations, in-situ vibrational and electronic spectroscopy, and a suite of other advanced materials characterization techniques to understand and ultimately leverage the phenomena more broadly into better-controlled electrolysis systems.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.

电化学使使用电能驱动化学反应。由于它们与可再生电力基础设施的兼容性，这些反应越来越有趣。反应是通过分子与称为电极的材料的相互作用而发生的，该材料保持在施加的电压下，当分子接触其表面时，可以表现出催化特性。该项目将研究一种现象，其中电极材料不是静态的，而是产生介导催化反应的腐蚀产物。在许多情况下，腐蚀被视为有害过程。但是，在这个项目中，研究人员旨在有目的和有效地使用腐蚀产品。该机制尚未得到充分的理解，并获得了控制和利用它可能会影响电化学系统的多种化学生产的能力。该项目中要研究的特定反应与生物质衍生的分子的转化有关，以使绿色燃料和化学前体与可生物降解的塑料相关。除了博士的预期收益。 PIS培训劳动力发展，将为本科生和教育材料建立研究机会，并为大型学生，科学家和非专家社区成员提供教育材料。正在进行的几项旨在支持的举措，而该项目将为当地社区大学教师提供新的研究经验机会，以帮助塑造未来的课程，并指导学生继续从两年到四年制学位课程。该项目的目的是了解该项目的程度在多大程度上减少了金属物质，从而通过降低了金属水合物或分解了摩尔氏菌的形成，可能会逐渐变细，可能会分解出摩尔群的形成。尽管传统上被视为有害的副反应，但该项目探讨了以下假设：这些阴极腐蚀产物可以介导均质减少，即使在某些情况下是主要机制。该假设将根据从天然电极材料或亚稳态的原位液相（如固体金属氢化物或碱合金）的异质电荷转移的可能机制进行评估。特定的反应性研究将涉及降低脱氟辛酸（LA）作为测试床。该分子源自可再生生物量，可以将其降低到几种有价值的产品中。 PI获得了初步证据表明，腐蚀产物介导可能涉及高度选择性的材料，这些材料可从LA中获得羟基胶合酸（可生物降解塑料的单体）和伽马谷酮（一种绿色溶液和生物燃料）。该计划是结合严格的动力学测量工具，量子化学计算，原位振动和电子光谱，以及一系列其他先进的材料表征技术，以理解和最终更广泛地利用现象，以更广泛地利用现象，以更加控制的电解系统，这些奖项通过NSF的法定任务和建立的依据，这是由NSF的范围进行了评估。 标准。