Computational prediction of hot-electron chemistry: Towards electronic control of catalysis

热电子化学的计算预测：迈向催化的电子控制

• 批准号: MR/S016023/1
• 负责人: Reinhard J. Maurer
• 金额: $ 149.23万
• 依托单位: University of Warwick
• 依托单位国家: 英国
• 项目类别: Fellowship
• 财政年份: 2019
• 资助国家: 英国
• 起止时间: 2019 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=MR%2FS016023%2F1
• 关键词: Computational; prediction; hot; electron; chemistry

Higher living standards and a growing world population are the drivers behind continuous increases in greenhouse gas emission and industrial energy use. This provides growing pressure on chemical industries to develop more sustainable and efficient chemical transformations based on innovative new technologies. Light-driven plasmonic catalysis offers a promising route to more sustainable and energy efficient chemical transformations than conventional industrial-scale catalysis by replacing petrochemical reactants and energy sources with abundant feedstocks such as carbon dioxide from the atmosphere and renewable energy from sunlight. In addition, light energy can selectively be transferred via excited electrons in metal nanoparticles, so-called "hot" electrons, to molecules and enables more specific chemical reactions than conventional catalysis, potentially increasing yield and decreasing unwanted side products. Underlying this unconventional form of chemistry is the intricate coupling of light, hot electrons, and reactant molecules, the lack of understanding of which has inhibited systematic design and study of reaction parameters such as particle size, shape, and optimal light exposure. A predictive theory of hot-electron chemistry will support the adaptation of this technology in the chemical industry, which holds the potential to significantly reduce the industry's carbon footprint.The aim of this project is to develop and exploit a computational simulation framework to understand, predict, and design light-driven chemical reactions on light-sensitive metallic nanoparticles and surfaces, so-called plasmonic nanocatalysts. The vision behind this fellowship is to provide quantum theoretical methods that fill a conceptual and methodological gap by providing accurate and feasible computational prediction of experimentally measurable chemical reaction rates as a function of catalyst design parameters relevant to the real-world application of this technology. In synergy with experimental project partners, the fellow will lead a research team of 2 postdoctoral researchers to develop highly efficient computational chemistry methodology, which will be applied to scrutinize mechanistic proposals, support and guide experimental efforts on light-driven plasmonic carbon dioxide reduction chemistry, and to construct reaction rate models relevant to improve the industrial viability of this technology. The aim is to provide a step-change in the mechanistic understanding of light-driven plasmonic reduction catalysis on the example of carbon monoxide and carbon dioxide transformation to enable rational design of catalyst materials with wide implications for continuous photochemistry and electrochemistry applications in industry. These applications will be explored by continuous engagement efforts of the fellow with leading chemical and petrochemical companies. With this project, the fellow will establish an international track record by fostering existing and establishing new collaborations with the goal to become a recognized researcher in this comparably young field.

生活水平的提高和世界人口的增长是温室气体排放和工业能源使用持续增加的驱动因素。这给化学工业带来了越来越大的压力，要求它们基于创新的新技术开发更可持续和更有效的化学转化。与传统工业规模的催化相比，光驱动等离子体催化提供了一条更可持续、更节能的化学转化途径，它用丰富的原料（如大气中的二氧化碳和来自阳光的可再生能源）取代石化反应物和能源。此外，光能可以选择性地通过金属纳米粒子中的激发态电子（即所谓的“热”电子）转移到分子中，从而实现比传统催化更具体的化学反应，从而潜在地提高产量并减少不需要的副产物。这种非常规化学形式的基础是光、热电子和反应物分子的复杂耦合，缺乏对其的理解抑制了系统设计和研究反应参数，如颗粒大小、形状和最佳光照。热电子化学的预测理论将支持该技术在化学工业中的应用，这有可能显著减少该行业的碳足迹。该项目的目的是开发和利用一个计算模拟框架来理解、预测和设计光敏金属纳米颗粒和表面上的光驱动化学反应，即所谓的等离子体纳米催化剂。该奖学金背后的愿景是提供量子理论方法，通过提供准确和可行的计算预测，通过实验可测量的化学反应速率作为与该技术的实际应用相关的催化剂设计参数的函数，填补概念和方法上的空白。该研究员将与实验项目合作伙伴共同领导一个由2名博士后组成的研究团队，开发高效的计算化学方法，用于审查机制提案，支持和指导光驱动等离子体二氧化碳还原化学的实验工作，并构建相关的反应速率模型，以提高该技术的工业可行性。其目的是以一氧化碳和二氧化碳转化为例，为光驱动等离子体还原催化的机理理解提供一个台阶变化，以使催化剂材料的合理设计具有广泛意义的连续光化学和电化学工业应用。这些应用将通过该研究员与领先的化学和石化公司的持续合作来探索。通过这个项目，该研究员将通过促进现有的和建立新的合作来建立一个国际记录，目标是成为这个相对年轻的领域公认的研究人员。

项目成果

Design Principles for Metastable Standing Molecules.

• DOI: 10.1021/acs.jpcc.2c01514
• 发表时间: 2022-04-21
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Arefi, Hadi H.;Corken, Daniel;Tautz, F. Stefan;Maurer, Reinhard J.;Wagner, Christian
• 通讯作者: Wagner, Christian

Coexistence of carbonyl and ether groups on oxygen-terminated (110)-oriented diamond surfaces

• DOI: 10.1038/s43246-022-00228-4
• 发表时间: 2022-01-28
• 期刊: COMMUNICATIONS MATERIALS
• 影响因子: 7.8
• 作者: Chaudhuri, Shayantan;Hall, Samuel J.;Maurer, Reinhard J.
• 通讯作者: Maurer, Reinhard J.

Plasmonic enhancement of molecular hydrogen dissociation on metallic magnesium nanoclusters.

• DOI: 10.1039/d1nr02033a
• 发表时间: 2021-03
• 期刊: Nanoscale
• 影响因子: 6.7
• 作者: O. A. Douglas-Gallardo;C. Box;R. Maurer

Zinc-Porphine on Coinage Metal Surfaces: Adsorption Configuration and Ligand-Induced Central Atom Displacement

• DOI: 10.1021/acs.jpcc.3c00232
• 发表时间: 2023-04-10
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Baklanov，Aleksandr;Kuechle，Johannes T.;Auwaerter，Willi
• 通讯作者: Auwaerter，Willi

Determining the Effect of Hot Electron Dissipation on Molecular Scattering Experiments at Metal Surfaces.

• DOI: 10.1021/jacsau.0c00066
• 发表时间: 2021-02-22
• 期刊: JACS Au
• 影响因子: 8
• 作者: Box CL;Zhang Y;Yin R;Jiang B;Maurer RJ
• 通讯作者: Maurer RJ