Facilitating the Rational Design of Active Sites for the Oxygen Evolution Reaction on 3d Transition Metal Oxide Catalysts

促进 3d 过渡金属氧化物催化剂析氧反应活性位点的合理设计

• 批准号: 399915593
• 负责人: Professor Dr. Karsten Reuter
• 金额: --
• 依托单位: Abteilung Theorie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/399915593?language=en
• 关键词: Facilitating; Rational; Design; Active; Sites

The proposed work will involve the development of new methods as well as the application of existing methods to obtain an understanding of how the activity for the oxygen evolution reaction (OER) of an active site on a 3D transition metal oxide surface is related to the structure (geometry and composition) of the active site. This would enable us to identify the properties of an active site leading to highest OER activity, as well as the mechanism by which the reaction occurs on such a site. This would provide valuable guidance for future experimental and computational search for a practical heterogeneous oxygen evolution catalyst. Additionally we will seek an understanding of this structure-activity relationship at the quantum chemical level. Periodic density functional theory (DFT) calculations will be used to determine the energetics of catalytic intermediates and rate constants for reaction steps which will then be used in a kinetic model to predict the turnover frequency and rate controlling step of the catalytic cycle for several different mechanisms. The calculations will include interactions with a continuum model of the electrolyte and will be performed on charged as well as neutral states of the active site. This latter task will require the development of a method for calculating free energies of charged active sites within the framework of periodic DFT, a frequently encountered situation in catalysis at the solid-liquid interface for which a universally applicable and computationally inexpensive approach does not currently exist. Novel constraining methods for examining the local electronic structure of the active site that were previously developed in our group will be used and further developed to understand how the electronic structure varies across the different metal oxides and how this relates to the catalytic activity.

提出的工作将涉及新方法的发展以及现有方法的应用，以了解如何了解3D过渡金属氧化物表面上活性位点的氧气演化反应（OER）与活性位点的结构（几何和组成）有关。这将使我们能够确定活性位点的特性，从而导致OER活性最高，以及在这种位点上发生反应的机制。这将为未来的实验和计算搜索提供宝贵的指导，以实现实用的异质氧演化催化剂。此外，我们将在量子化学水平上寻求对这种结构活性关系的理解。周期性密度功能理论（DFT）计算将用于确定反应步骤的催化中间体和速率常数的能量，然后将其用于动力学模型，以预测几种不同机制的催化周期的转离频率和控制速率的步骤。计算将包括与电解质的连续模型的相互作用，并将在活性位点的带电和中性状态上进行。后一个任务将需要开发一种方法来计算周期性DFT框架内带电的活动站点的自由能，这是固体液体界面处的催化中经常遇到的情况，目前不存在一种普遍适用和计算廉价的方法。将使用并进一步开发用于研究以前在我们组中开发的活性位点的局部电子结构的新型约束方法，以了解电子结构如何在不同的金属氧化物中变化以及与催化活性的关系。