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CAREER: Revealing spin-state-dependent reactivity in open-shell single atom catalysts with systematically-improvable computational tools

职业：利用可系统改进的计算工具揭示开壳单原子催化剂中自旋态依赖的反应性

基本信息

批准号：
1846426
负责人：
Heather Kulik
金额：
$ 59.37万
依托单位：
Massachusetts Institute of Technology
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2019
资助国家：
美国
起止时间：
2019-06-01 至 2025-05-31
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1846426&HistoricalAwards=false
关键词：
CAREER Revealing spin state dependent

项目摘要

The project focuses on selective chemical conversion of hydrocarbons found in natural gas to products of value as intermediates in the manufacture of a wide range of chemicals and fuels. To that end, the project will investigate a new class of catalytic materials known as single atom catalysts (SACs), specifically by developing computational modeling tools that will aid the discovery and design of SACs. The resulting fundamental understanding will enable rational design of robust and stable SACs for targeted challenging chemical transformations, thus providing the chemical and petroleum industries with new catalysts needed to maintain our Nation's competitiveness in the chemicals and energy sectors of the economy. These research advances will form the basis of quest-based workshop activities that teach catalysis and computation to Boston-area grade 6-12 students, advancing excitement about STEM. Single atom catalysts (SACs) are emergent catalytic materials that promise to unite the scalability of heterogeneous catalysts with the activity, selectivity, and atom-economy of homogeneous catalysts, but the reactivity of SACs is poorly understood. Short-lived, sub-nanoscale SAC active sites challenge the resolution of experimental spectroscopic techniques, making computational modeling essential to building understanding of the mechanism of SAC catalysts. The project will advance understanding of how SAC structure imparts unique reactivity for critical transformations (i.e., selective partial hydrocarbon oxidation) through systematically improvable computational modeling. Although SACs are poised as a new paradigm in selective but scalable catalysts, the very features that make SACs reactive for essential catalytic transformations also make conventional computational catalysis tools (i.e., semi-local density functional theory or DFT) ill suited to predictive SAC study. This project will identify and implement needed systematic advances beyond semi-local DFT for predictive modeling of how ligand-field-influenced spin- and oxidation-state of quantum-confined metals at SAC active sites alters reactivity. Advancement of fundamental understanding of single atom catalysts will be achieved through three aims: 1) quantifying spin state-dependent reactivity of SACs for selective transformations, 2) understanding how support identity and active site configuration/disorder influences electronic structure and reactivity of SACs, and 3) developing descriptors to predict and optimize SAC activity and stability. This will enable the tailoring of SACs for selectivity, activity, and scalability needed to address the "holy grail" challenge in catalysis of partial alkane oxidation. It will overhaul simulation methods for studying unique SAC electronic structure properties, both providing accurate predictions and incorporating disorder effects in rational SAC design. Development of SACs robust for the industrial scale with earth abundant, atom economical metal use will have a profound impact on the environment. The research advances will be integrated into outreach activities in a twice-yearly workshop that teaches catalysis and computation to grade 6-12 students, advancing excitement about STEM. The workshop will introduce catalysis and bonding concepts through 3D models, and students will design catalysts in a quest game adapted from software developed as part of this project. The program will be assessed and improved by quizzes before/after the workshop. Teaching materials for classroom instruction and web tutorials posted on the PI's website and MIT OpenCourseWare will amplify the reach of the education program. This program will benefit society by advancing excitement about STEM through immersive and research-derived tools.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.

该项目的重点是将天然气中的碳氢化合物选择性地化学转化为有价值的产品，作为制造各种化学品和燃料的中间体。为此，该项目将研究一类新的催化材料，称为单原子催化剂（SAC），特别是通过开发有助于发现和设计SAC的计算建模工具。由此产生的基本理解将使强大和稳定的SAC的合理设计，有针对性的具有挑战性的化学转化，从而提供化学和石油工业所需的新催化剂，以保持我们国家的竞争力在化学和能源经济部门。这些研究进展将构成基于任务的研讨会活动的基础，这些活动将向波士顿地区6-12年级的学生教授催化和计算，从而提高对STEM的兴奋程度。单原子催化剂（SACs）是一种新兴的催化材料，有望将多相催化剂的可扩展性与均相催化剂的活性、选择性和原子经济性相结合，但对SACs的反应性知之甚少。短寿命的亚纳米SAC活性位点挑战了实验光谱技术的分辨率，使得计算建模对于建立对SAC催化剂机理的理解至关重要。该项目将促进对SAC结构如何赋予关键转化独特反应性的理解（即，选择性部分烃氧化）。尽管SAC作为选择性但可扩展的催化剂的新范例而蓄势待发，但使SAC对基本催化转化具有反应性的特征也使常规的计算催化工具（即，半局域密度泛函理论或DFT）不适合预测SAC研究。该项目将确定并实施所需的系统性进展，超越半局部DFT，用于预测SAC活性位点的量子限制金属的配体场影响自旋和氧化态如何改变反应性的建模。推进单原子催化剂的基本理解将通过三个目标实现：1）量化选择性转化的SAC的自旋状态依赖的反应性，2）理解支持身份和活性位点配置/无序如何影响SAC的电子结构和反应性，以及3）开发描述符来预测和优化SAC活性和稳定性。这将使得能够针对解决部分烷烃氧化催化中的“圣杯”挑战所需的选择性、活性和可扩展性来定制SAC。它将彻底检查用于研究独特SAC电子结构特性的模拟方法，既提供准确的预测，又将无序效应纳入合理的SAC设计。开发具有地球丰富、原子经济的金属使用的工业规模的SAC将对环境产生深远的影响。这些研究进展将被纳入一年两次的研讨会的推广活动中，该研讨会向6-12年级的学生教授催化和计算，促进对STEM的兴奋。该研讨会将通过3D模型介绍催化和粘合概念，学生将设计催化剂在一个探索游戏改编自软件开发作为该项目的一部分。在研讨会之前/之后，将通过测验来评估和改进该计划。在PI网站和麻省理工学院开放课程软件上发布的课堂教学和网络教程的教学材料将扩大教育计划的覆盖范围。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

期刊论文数量（25）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Putting Density Functional Theory to the Test in Machine-Learning-Accelerated Materials Discovery

DOI：
10.1021/acs.jpclett.1c00631
发表时间：
2021-05-11
期刊：
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
影响因子：
5.7
作者：
Duan, Chenru;Liu, Fang;Kulik, Heather J.
通讯作者：
Kulik, Heather J.

Mechanistic Insights into Substrate Positioning That Distinguish Non-heme Fe(II)/α-Ketoglutarate-Dependent Halogenases and Hydroxylases

DOI：
10.1021/acscatal.2c06241
发表时间：
2023-02-03
期刊：
ACS CATALYSIS
影响因子：
12.9
作者：
Kastner, David W.;Nandy, Aditya;Kulik, Heather J.
通讯作者：
Kulik, Heather J.

Representations and strategies for transferable machine learning improve model performance in chemical discovery

可迁移机器学习的表示和策略提高了化学发现中的模型性能

DOI：
10.1063/5.0082964
发表时间：
2022
期刊：
The Journal of Chemical Physics
影响因子：
0
作者：
Harper, Daniel R.;Nandy, Aditya;Arunachalam, Naveen;Duan, Chenru;Janet, Jon Paul;Kulik, Heather J.
通讯作者：
Kulik, Heather J.

The Effect of Hartree-Fock Exchange on Scaling Relations and Reaction Energetics for C–H Activation Catalysts