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.

该奖项是根据2021年《美国救援计划法》（公法117-2）全部或部分资助的，氢是一种多功能，能量浓缩的天然气，可以用作许多应用中的化石燃料的替代品，包括运输和发电。然而，广泛采用氢燃料的限制是由于无法在精心控制的工业环境外安全地存储和运输氢气。该项目将研究一种有趣的化学现象，称为“分子软木塞效应”，该现象可能被证明可作为一种氢气存储机制。当氢气（双原子氢或H2）与一种称为单原子合金的材料相互作用时，已经观察到分子软糖效应。单原子合金由相对惰性的高贵金属表面组成，并散布着催化活性金属（如铂和钯）的单个原子。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打破。然后，单个氢原子溢出在惰性金属表面上。可以添加优先结合催化金属的“软木塞”分子，以防止氢原子改革气态氢。可以安全地以这种方式存储氢，直到温度升高以去除软木分子并将氢气从表面释放。必须开发对整个分子切割过程的基本见解，以充分实现单原子合金氢储存的潜力。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。该项目还包括一项旨在使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的教育计划。将开发独立的教育材料，以使任何化学讲师，无论使用计算方法的舒适性如何，都可以将计算化学模块整合到其课程中。 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.引入钯/铜或铂/铜单原子合金的双原子氢会在地表上吸附，在该表面上，催化活性金属将裂解氢 - 氢键。解离的原子氢溢出在贵族金属表面上。随后对催化活性金属中毒配体的选择性吸附，可防止解离的氢解吸和改革双原子氢。因此，该配体是“分子软木塞”，直到加热以解离配体，从而将氢气从表面释放。这种现象可能会在氢存储应用中利用。但是，单原子合金是一种相对较新的材料，而涉及分子软木塞效应的许多因素尚不清楚。因此，研究计划旨在（1）产生有关分子软木与表面如何相互作用的基本知识，（2）探索各种分子软木塞以氢存储的生存能力，以及（3）检查分子软木胶对单个ATOM合金聚集的影响。将采用最先进的计算方法，包括密度功能理论计算和动力学蒙特卡洛模拟，以揭示氢溢出的基于的分子水平现象以及单原子合金的解吸。通过扫描隧道显微镜和温度编程的解吸研究将通过协作进行实验验证。该项目的结果有可能推进氢存储技术，并将与界面工程和异源性催化研究社区广泛相关。该奖项反映了NSF的法定任务，并被认为是通过基金会的知识分子优点和更广泛的影响审查标准来通过评估来通过评估来支持的。

项目成果

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
• 期刊: ACS Spring 2024
• 作者: Santos, A;Jensen, L;Knizia, G
• 通讯作者: Knizia, G

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
• 期刊: ACS Spring 2024
• 作者: Simpson, S.

A Computational Experiment Introducing Undergraduates to Geometry Optimizations, Vibrational Frequencies, and Potential Energy Surfaces

向本科生介绍几何优化、振动频率和势能面的计算实验

• DOI: 10.1021/acs.jchemed.2c01129
• 发表时间: 2023
• 期刊: Journal of Chemical Education
• 影响因子: 3
• 作者: Hanson, Matthew D.;Miller, Daniel P.;Kondeti, Cholavardhan;Brown, Adam;Zurek, Eva;Simpson, Scott
• 通讯作者: Simpson, 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
• 期刊: Pacifichem 2021
• 作者: Simpson, Scott

Comparing experimental and computational approaches for studying the binding of N-heterocyclic carbenes

比较研究 N-杂环卡宾结合的实验方法和计算方法

• 发表时间: 2024
• 期刊: ACS Spring 2024
• 作者: Santos, A;Simpson, S
• 通讯作者: Simpson, S