CAREER: SusChEM: Unlocking local solvation environments for energetically efficient hydrogenations with quantum chemistry

职业：SusChEM：通过量子化学解锁局部溶剂化环境，实现高能高效氢化

• 批准号: 1653392
• 负责人: John Keith
• 金额: $ 50万
• 依托单位: University of Pittsburgh
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-02-01 至 2024-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1653392&HistoricalAwards=false
• 关键词: CAREER; SusChEM; Unlocking; local; solvation

The project addresses the production of carbon-neutral liquid fuels via electrocatalytic reduction of the greenhouse gas carbon dioxide (CO2) to methanol. Specifically, the study seeks to improve the efficiency and selectivity of current solvent-based electrochemical processes by advancing understanding of how aqueous electrolytes participate in the overall reaction mechanisms at the atomic scale. The research will be coupled with educational thrusts that engage students in grades 8-12 in learning about renewable energy catalysis and computational chemistry.The focus of the study will be to integrate high-level electronic structure theory, molecular dynamics, and machine learning to quantitatively understand how interactions between solvent molecules, salts, and co-solutes (i.e. "local solvation environments") regulate fundamental mechanisms of CO2 reduction (CO2R) into fuels. Four basic scientific questions will be addressed related to CO2R in the presence of aromatic N-heterocycles, here studied in the form of molecules and as nitrogen-doped carbon electrodes. These are 1) the identification of the most likely chemical functionalities (i.e. Lewis base, Brønsted acid, H-atom donor, hydride donor) that participate in energetically efficient CO2R into methanol; 2) quantitative predictions of the free energy barriers for different CO2 hydrogenation processes in different local solvation environments; 3) refined understanding of the level of computational modeling needed to reliably predict hydrogenation thermodynamics and kinetics in realistic electrochemical environments; and 4) generalized insight into the degree to which local solvation environments can be tuned to enhance the conversion of low-value carbon-containing feedstocks to liquid fuels. Graduate and undergraduate students will develop educational modules that combine concepts in renewable energy and introduce computational chemistry modeling. These modules will then be tested to determine their capacity to engage and excite students in the Pittsburgh Public School District about opportunities in STEM fields.

该项目通过将温室气二氧化碳（CO2）的电催化降低降低到甲醇来解决碳中性液体燃料的生产。具体而言，该研究试图通过促进对水溶液如何参与原子量表的总体反应机制来提高当前基于溶液的电化学过程的效率和选择性。这项研究将与教育推力相结合，使学生参与8 - 12年级的学习，以学习可再生能源催化剂和计算化学。该研究的重点将是整合高级电子结构理论，分子动力学和机器学习，以定量地在溶解分子，盐和共同体之间的相互作用（I.E.2）之间的相互作用， （CO2R）成燃料。在存在芳香族N-杂环的情况下，将解决与CO2R有关的四个基本科学问题，在这里以分子的形式和氮掺杂的碳电极进行了研究。这些是1）鉴定最可能的化学功能（即刘易斯碱，布朗斯特酸，h原子供体，氢供体），该功能参与有效的CO2R进入甲醇； 2）在不同局部溶液环境中不同二氧化碳氢化过程的自由能壁垒的定量预测； 3）精致的本科生将开发教育模块，以结合可再生能源的概念并引入计算化学建模。然后，将对这些模块进行测试，以确定他们在匹兹堡公立学区吸引和激动人心的学生有关STEM领域机会的能力。

项目成果

Thermodynamic Hydricities of Biomimetic Organic Hydride Donors

• DOI: 10.1021/jacs.7b13526
• 发表时间: 2018-04-04
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Ilic, Stefan;Kadel, Usha Pandey;Glusac, Ksenija D.
• 通讯作者: Glusac, Ksenija D.

First-principles modeling of chemistry in mixed solvents: Where to go from here?

• DOI: 10.1063/1.5143207
• 发表时间: 2020-04
• 期刊: The Journal of chemical physics
• 作者: Alex M. Maldonado;Yasemin Basdogan;J. T. Berryman;S. Rempe;J. Keith

Quantifying Uncertainties in Solvation Procedures for Modeling Aqueous Phase Reaction Mechanisms

• DOI: 10.1021/acs.jpca.0c08961
• 发表时间: 2021-01-04
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY A
• 影响因子: 2.9
• 作者: Maldonado, Alex M.;Hagiwara, Satoshi;Keith, John A.
• 通讯作者: Keith, John A.

Benchmarking Computational Alchemy for Carbide, Nitride, and Oxide Catalysts

• DOI: 10.1002/adts.201800142
• 发表时间: 2019-04-01
• 期刊: ADVANCED THEORY AND SIMULATIONS
• 影响因子: 3.3
• 作者: Griego, Charles D.;Saravanan, Karthikeyan;Keith, John A.
• 通讯作者: Keith, John A.

Quantum alchemy beyond singlets: Bonding in diatomic molecules with hydrogen

单线态之外的量子炼金术：双原子分子与氢的键合

• DOI: 10.1063/5.0079487
• 发表时间: 2022
• 期刊: The Journal of Chemical Physics
• 作者: Eikey, Emily A.;Maldonado, Alex M.;Griego, Charles D.;von Rudorff, Guido Falk;Keith, John A.
• 通讯作者: Keith, John A.