CAREER: Investigating the Molecular Corking Effect for Potential Hydrogen Storage

职业：研究潜在储氢的分子栓塞效应

• 批准号: 2142874
• 负责人: Scott Simpson
• 金额: $ 54.49万
• 依托单位: Saint Bonaventure University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-02-01 至 2027-01-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2142874&HistoricalAwards=false
• 关键词: CAREER; Investigating; Molecular; Corking; Effect

This award is funded in whole or in part under the American Rescue Plan Act of 2021 (Public Law 117-2)Hydrogen is a versatile, energy-dense gas that can be used as an alternative to fossil fuels in many applications, including transportation and power generation. However, widespread adoption of hydrogen fuels is limited, in part, by the inability to safely store and transport hydrogen gas outside of carefully controlled industrial environments. This project will study an intriguing chemical phenomenon called the "molecular corking effect," which may prove useful as a hydrogen gas storage mechanism. The molecular corking effect has been observed when hydrogen gas (diatomic hydrogen or H2) interacts with a class of materials called single-atom alloys. Single-atom alloys consist of a relatively inert noble metal surface interspersed with single atoms of catalytically-active metals such as platinum and palladium. When diatomic hydrogen gas contacts the single-atom alloy, the bond between the two hydrogen atoms is broken by the catalytically-active metal. The individual hydrogen atoms then spill over on the inert metal surface. A "cork" molecule that preferentially binds to the catalytically-active metal can be added to prevent the hydrogen atoms from reforming gaseous hydrogen. Hydrogen can be safely stored in this manner until the temperature is increased to remove the cork molecule and release the hydrogen gas from the surface. Fundamental insights into the entire molecular corking process must be developed to fully realize the potential of single-atom alloy hydrogen storage. The research objectives of this project will examine how molecular corks interact with single-atom alloys and describe the chemical characteristics of effective molecular corks. The project also includes an education plan focused on preparing students to integrate computational chemistry and experimental research in their pursuit of chemical and physical knowledge. Self-contained educational materials will be developed such that any chemistry instructor, regardless of comfort with computational methods, can integrate computational chemistry modules into their curriculum. These materials, along with outreach activities at local high schools, will encourage the participation of students from primarily undergraduate institutions and other resource-limited environments in computational chemistry-driven research.The goal of this project, led by Dr. Scott Simpson at St. Bonaventure University, is to explore the limits of the "molecular corking effect" to control hydrogen spillover on single-atom alloys. Diatomic hydrogen introduced to a palladium/copper or platinum/copper single-atom alloy will adsorb at the surface, where the hydrogen-hydrogen bond will be cleaved by the catalytically-active metal. The dissociated atomic hydrogen spills over on the noble metal surface. Subsequent selective adsorption of a poisoning ligand to the catalytically-active metal prevents the dissociated hydrogen from desorbing and reforming diatomic hydrogen. This ligand, thus, serves as a "molecular cork" until heat is applied to dissociate the ligand, liberating hydrogen gas from the surface. This phenomenon can potentially be leveraged in hydrogen storage applications. However, single-atom alloys are a relatively new class of materials, and the many factors governing the molecular corking effect are unknown. Accordingly, the research plan is designed to (1) generate fundamental knowledge of how molecular corks interact with surfaces, (2) explore the viability of various molecular corks for hydrogen storage, and (3) examine the impacts of molecular cork adsorption on single-atom alloys aggregation. State-of-the-art computational methods, including density functional theory calculations and kinetic Monte Carlo simulations, will be employed to reveal the molecular-level phenomena underlying hydrogen spillover and desorption from single-atom alloys. Experimental validation via scanning tunneling microscopy and temperature-programed desorption studies will be conducted through collaborations. The outcomes of this project have the potential to advance hydrogen storage technologies and will be broadly relevant to the interfacial engineering and heterogenous catalysis research communities.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.

该奖项的全部或部分资金根据《2021 年美国救援计划法案》（公法 117-2）提供。氢气是一种多功能、能量密集的气体，可在许多应用中用作化石燃料的替代品，包括运输和运输发电。然而，氢燃料的广泛采用受到限制，部分原因是无法在严格控制的工业环境之外安全地储存和运输氢气。该项目将研究一种有趣的化学现象，称为“分子栓塞效应”，该现象可能被证明可用作氢气储存机制。当氢气（双原子氢或 H2）与一类称为单原子合金的材料相互作用时，可以观察到分子栓塞效应。单原子合金由相对惰性的贵金属表面组成，表面散布有催化活性金属（例如铂和钯）的单原子。当双原子氢气接触单原子合金时，两个氢原子之间的键被催化活性金属破坏。然后单个氢原子溢出到惰性金属表面。可以添加优先与催化活性金属结合的“软木”分子，以防止氢原子重新形成气态氢。氢气可以通过这种方式安全储存，直到温度升高以去除软木分子并从表面释放氢气。必须开发对整个分子焦化过程的基本见解，以充分发挥单原子合金储氢的潜力。该项目的研究目标将研究分子软木塞如何与单原子合金相互作用，并描述有效分子软木塞的化学特性。该项目还包括一项教育计划，重点是让学生在追求化学和物理知识的过程中整合计算化学和实验研究。将开发独立的教育材料，以便任何化学教师，无论是否熟悉计算方法，都可以将计算化学模块整合到他们的课程中。这些材料以及当地高中的推广活动将鼓励主要来自本科院校和其他资源有限环境的学生参与计算化学驱动的研究。该项目的目标是由圣路易斯大学的 Scott Simpson 博士领导。博纳文图尔大学正在探索“分子塞克效应”的极限，以控制单原子合金上的氢溢出。引入钯/铜或铂/铜单原子合金的双原子氢将吸附在表面，其中氢-氢键将被催化活性金属裂解。离解的原子氢溢出到贵金属表面。随后中毒配体选择性吸附到催化活性金属上，防止解离的氢解吸和重整双原子氢。因此，该配体充当“分子软木塞”，直到施加热量以解离配体，从表面释放氢气。这种现象有可能在储氢应用中得到利用。然而，单原子合金是一类相对较新的材料，控制分子堵塞效应的许多因素尚不清楚。因此，该研究计划旨在（1）产生分子软木如何与表面相互作用的基础知识，（2）探索各种分子软木用于储氢的可行性，以及（3）研究分子软木吸附对单层软木的影响。原子合金聚集。最先进的计算方法，包括密度泛函理论计算和动力学蒙特卡罗模拟，将用于揭示单原子合金中氢溢出和解吸的分子水平现象。将通过合作进行通过扫描隧道显微镜和程序升温解吸研究进行的实验验证。该项目的成果有潜力推进储氢技术，并将与界面工程和多相催化研究界广泛相关。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力优势和更广泛的评估进行评估，被认为值得支持。影响审查标准。

项目成果

The Search for Molecular Corks Beyond Carbon Monoxide: A Quantum Mechanical Study of N-Heterocyclic Carbene Adsorption on Pd/Cu(111) and Pt/Cu(111)

寻找一氧化碳之外的分子软木塞：N-杂环卡宾在 Pd/Cu(111) 和 Pt/Cu(111) 上吸附的量子力学研究

• 发表时间: 2022-03
• 期刊: ACS Spring 2022
• 作者: Simpson; Scott
• 通讯作者: Scott

Search for molecular corks beyond carbon monoxide: A quantum mechanical study of N-heterocyclic carbene adsorption on Pd/Cu(111) and Pt/Cu(111) single atom alloys

寻找一氧化碳之外的分子软木塞：Pd/Cu(111)和Pt/Cu(111)单原子合金上N-杂环卡宾吸附的量子力学研究

• 发表时间: 2021-12
• 期刊: Pacifichem 2021
• 作者: Simpson; Scott
• 通讯作者: Scott

Understanding bonding of N-heterocyclic carbenes on Pd/Cu(111) single atom alloys via non-local density functional theory to store hydrogen via the molecular corking effect

通过非局域密度泛函理论了解N-杂环卡宾在Pd/Cu(111)单原子合金上的键合，通过分子焦化效应储存氢

• 发表时间: 2024-03
• 期刊: ACS Spring 2024
• 作者: Simpson; S.
• 通讯作者: S.

Multivariable Model Fitting as Applied to Air, a Physical Chemistry Experiment

应用于空气的多变量模型拟合，物理化学实验

• DOI: 10.1021/acs.jchemed.1c01241
• 发表时间: 2022-05
• 期刊: Journal of Chemical Education
• 影响因子: 3
• 作者: Antle, Jonathan P.;Godbout, Jerry T.;Simpson, Scott
• 通讯作者: Simpson, Scott

Bonding of N-heterocyclic carbenes on metal nanoparticles: A computational approach to characterizing stability

N-杂环卡宾在金属纳米颗粒上的键合：表征稳定性的计算方法

• 发表时间: 2024-03
• 期刊: ACS Spring 2024
• 作者: Santos, A;Jensen, L;Knizia, G
• 通讯作者: Knizia, G