Molecular Characterization of Water Oxidation in Metal-Organic Frameworks through Computer Simulations

通过计算机模拟对金属有机框架中的水氧化进行分子表征

• 批准号: 1704063
• 负责人: Francesco Paesani
• 金额: $ 44.35万
• 依托单位: University of California-San Diego
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1704063&HistoricalAwards=false
• 关键词: Molecular; Characterization; Water; Oxidation; Metal

Molecular Characterization of Water Oxidation in Metal-Organic Frameworks through Computer SimulationsComputer simulations have become a powerful tool to gain critical insights into complex molecular processes, which are otherwise difficult to obtain by other means. However, achieving the necessary accuracy for realistic and predictive simulations is a challenge. In this project, Dr. Paesani and his group are developing and applying a novel and powerful simulation methodology to model water oxidation in a class of highly porous solids known as metal-organic frameworks (MOFs). Water oxidation is one of the key reactions in natural photosynthesis. Therefore, understanding the steps involved in water oxidation at the molecular level may aid in the development of artificial photosynthetic systems. MOFs are a relatively new class of materials and are ideal for these catalysts. The studies carried out by Dr. Paesani and his group are advancing both the theory and the computer modeling of MOFs and their chemistry, which are key to the rational development of new catalysts. In parallel with the research activities, an innovative education and outreach plan is being established to introduce freshman and sophomore undergraduate students to computational methods in chemistry and materials research. Dr. Paesani and his group are also promoting interest in STEM disciplines among underprivileged and underrepresented minority students through the development of summer exchange programs at the University of California - San Diego.The fundamental understanding of how to control water oxidation to molecular oxygen is a prerequisite for the development of artificial systems to harvest and convert solar energy as well as to enable visible-light-driven organic synthesis. It is well known that the availability of water as an electron donor opens up a wide variety of reductive processes that can be driven with electricity or sunlight. Since water is one of the ultimate products of fossil fuel combustion, the conversion of H2O molecules back into fuel involves thermodynamically uphill reactions that remove oxygen atoms. In this project, Dr. Paesani and his group are performing fundamental studies to investigate the elementary steps involved in water oxidation reactions in metal-organic frameworks (MOFs). MOFs are a relatively new class of porous materials with large surface areas that have already found application in gas storage (e.g., methane and hydrogen storage), carbon capture, hydrocarbon separation, chemical sensing, nonlinear optics, biomedical imaging, drug delivery, catalysis, electrical and proton conductivity, magnetism, and luminescence. Since MOF structure and physicochemical properties are highly tunable, MOFs represent promising platforms for building efficient functional devices for solar energy harvesting and conversion. Dr. Paesani and his group are developing and applying novel simulation methodologies that combine many-body representations of the molecular interactions with advanced techniques to describe chemical reactivity in the condensed phase to characterize the elementary steps associated with catalytic processes in MOFs. This information is key to the rational design of new MOF structures with properties specifically tailored for solar energy harvesting and conversion. The interdisciplinary nature of the research project represents an extraordinary opportunity for training at the interface of different disciplines, providing bridges and inter-connections between the fundamental laws of physics and the molecular properties of materials at the nanoscale. In this context, mentoring and outreach activities are specifically designed to promote science disciplines among high school and college students from underprivileged and underrepresented minorities through the development and implementation of summer exchange programs at UC San Diego.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.

通过计算机模拟对金属有机框架中的水氧化进行分子表征计算机模拟已成为获得对复杂分子过程的重要见解的强大工具，而这些过程很难通过其他方式获得。然而，实现现实和预测模拟所需的准确性是一个挑战。在这个项目中，Paesani 博士和他的团队正在开发并应用一种新颖且强大的模拟方法来模拟一类称为金属有机框架 (MOF) 的高多孔固体中的水氧化。水氧化是自然光合作用的关键反应之一。因此，在分子水平上了解水氧化所涉及的步骤可能有助于人工光合作用系统的发展。 MOF 是一类相对较新的材料，是这些催化剂的理想选择。 Paesani 博士和他的团队进行的研究正在推进 MOF 及其化学的理论和计算机建模，这是合理开发新催化剂的关键。在开展研究活动的同时，我们还制定了一项创新教育和推广计划，向本科生一年级和二年级学生介绍化学和材料研究的计算方法。 Paesani 博士和他的团队还通过在加州大学圣地亚哥分校开展暑期交换项目，提高贫困和代表性不足的少数族裔学生对 STEM 学科的兴趣。对如何控制水氧化成分子氧的基本了解是先决条件用于开发人工系统来收集和转换太阳能以及实现可见光驱动的有机合成。众所周知，水作为电子供体的可用性开启了各种可以用电力或阳光驱动的还原过程。由于水是化石燃料燃烧的最终产物之一，因此 H2O 分子转化回燃料涉及热力学上的艰苦反应，以去除氧原子。在这个项目中，Paesani 博士和他的团队正在进行基础研究，以研究金属有机框架 (MOF) 中水氧化反应所涉及的基本步骤。 MOF 是一类相对较新的具有大表面积的多孔材料，已在气体储存（例如甲烷和氢气储存）、碳捕获、碳氢化合物分离、化学传感、非线性光学、生物医学成像、药物输送、催化、电导率和质子导率、磁性和发光性。由于 MOF 结构和物理化学性质高度可调，MOF 代表了构建用于太阳能收集和转换的高效功能器件的有前景的平台。 Paesani 博士和他的团队正在开发和应用新颖的模拟方法，该方法将分子相互作用的多体表示与先进技术相结合，以描述凝聚相中的化学反应性，从而表征与 MOF 催化过程相关的基本步骤。这些信息是合理设计新型 MOF 结构的关键，该结构具有专门为太阳能收集和转换而定制的特性。该研究项目的跨学科性质代表了在不同学科交叉点进行培训的绝佳机会，为物理基本定律和纳米尺度材料的分子特性之间提供了桥梁和相互联系。在此背景下，指导和外展活动专门旨在通过在加州大学圣地亚哥分校制定和实施暑期交换项目，促进来自贫困和代表性不足的少数族裔的高中生和大学生的科学学科发展。该奖项反映了 NSF 的法定使命，并被视为值得通过使用基金会的智力优点和更广泛的影响审查标准进行评估来支持。

项目成果

A Ligand Field Molecular Mechanics Study of CO 2 ‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)

CO 2 的配体场分子力学研究 — 金属有机骨架 DUT — 8(Ni) 中的诱导呼吸

• DOI: 10.1002/adts.201900098
• 发表时间: 2019-07
• 期刊: Advanced Theory and Simulations
• 影响因子: 3.3
• 作者: Melix, Patrick;Paesani, Francesco;Heine, Thomas
• 通讯作者: Heine, Thomas

Unraveling the effect of defects, domain size, and chemical doping on photophysics and charge transport in covalent organic frameworks

揭示缺陷、畴尺寸和化学掺杂对共价有机框架中光物理和电荷传输的影响

• DOI: 10.1039/d1sc01262b
• 发表时间: 2021-05-13
• 期刊: Chemical Science
• 影响因子: 8.4
• 作者: Ghosh R;Paesani F
• 通讯作者: Paesani F

Connecting the dots for fundamental understanding of structure–photophysics–property relationships of COFs, MOFs, and perovskites using a Multiparticle Holstein Formalism

使用多粒子荷斯坦形式将这些点连接起来，从根本上理解 COF、MOF 和钙钛矿的结构、光物理学和性质关系

• 发表时间: 2023-02
• 期刊: Chemical Science
• 影响因子: 8.4
• 作者: Ghosh, Raja;Paesani, Francesco
• 通讯作者: Paesani, Francesco

Simulation Meets Experiment: Unraveling the Properties of Water in Metal–Organic Frameworks through Vibrational Spectroscopy

模拟与实验的结合：通过振动光谱揭示金属有机框架中水的性质

• DOI: 10.26434/chemrxiv.14370764.v1
• 发表时间: 2021-04-06
• 期刊: The Journal of Physical Chemistry C
• 作者: Kelly M. Hunter;Jackson C. Wagner;Mark Kalaj;Seth M. Cohen;Wei Xiong;F. Paesani
• 通讯作者: F. Paesani

Halogen bonding in UiO-66 frameworks promotes superior chemical warfare agent simulant degradation

UiO-66 框架中的卤素键可促进优异的化学战剂模拟降解

• DOI: 10.1039/c9cc00642g
• 发表时间: 2019-03
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Kalaj, Mark;Momeni, Mohammad R.;Bentz, Kyle C.;Barcus, Kyle S.;Palomba, Joseph M.;Paesani, Francesco;Cohen, Seth M.
• 通讯作者: Cohen, Seth M.