Molecule-Oxide Bond Formation

分子-氧化物键的形成

• 批准号: 238350734
• 负责人: Professor Dr. Jörg Libuda
• 金额: --
• 依托单位: Lehrstuhl für Katalytische Grenzflächenforschung
• 依托单位国家: 德国
• 项目类别: Research Units
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/238350734?language=en
• 关键词: Molecule; Oxide; Bond; Formation

The knowledge-based design of organic/oxide interfaces requires detailed insights into molecule-oxide bond formation. In close collaboration with its funCOS partner projects, funCOS 3 aims at providing this information, by combining two complementary surface spectroscopies, namely vibrational spectroscopy (infrared reflection absorption spectroscopy) and photoelectron spectroscopy (X-ray photoelectron spectroscopy using also synchrotron radiation, near edge X-ray absorption fine structure), in combination with other methods. Starting from studies in ultrahigh vacuum (UHV), we will bridge the gap between ideal and real conditions by exploring anchoring reactions at ambient pressure and in liquid environments (diffuse reflectance infrared Fourier transform spectroscopy, polarization-modulation IRAS, near ambient pressure XPS, electrochemical infrared reflection absorption spectroscopy). In addition, we will directly couple UHV experiments to reactivity studies and spectroscopy performed in liquid environments. The key information provided by funCOS 3 comprises reaction mechanisms, bonding geometries, the energetics, the kinetics, and the reversibility of bond formation. In the first funding period, we explored the fundamental aspects of molecular anchoring, using simple model surfaces, small test molecules, and simple porphyrin derivatives. Building on this foundation, the project will now take the next step and explore complex molecules, nanostructures surfaces, and realistic environments. We will shift our attention from MgO(100) towards the more complex cases of cobalt oxide (Co3O4, CoO) and titanium dioxide (TiO2), ideal test cases to explore molecular anchoring from UHV to liquid environments. Specifically, we will target five key challenges: (1) We will transfer knowledge and methods from small test molecules to functionalized porphyrin derivatives. Using our expertise with carboxylate anchors, we will tune substitution patterns, use multiple anchoring or employ chelating anchors to control the molecular orientation, the formation kinetics, and the stability. (2) We will explore the role of water in molecular anchoring. Starting from UHV studies to identify protons and OH groups in the anchored film, we will investigate the influence of H2O on bond formation and, finally, link these studies to spectroscopy at ambient pressure and in liquid environments. (3) Based on our comprehensive work on carboxylate anchors, we will explore alternative anchors to tune molecule-surface interactions (phosphonic acid, hydroxamic acid, hydroxyl, catechol). (4) We will explore concepts to tune intermolecular and molecule-surface interactions independently by substitution and metalation (by aromatic and steric interactions, polar groups, H bonds, metal coordination). (5) Finally, we will use this knowledge to explore selective anchoring to nanostructured oxides, e.g. by employing selective interactions of anchors with specific surface structures.

基于知识的有机/氧化物界面设计需要详细了解分子-氧化物键的形成。在与funCOS伙伴项目的密切合作下，funCOS 3旨在通过结合两种互补的表面光谱学，即振动光谱学（红外反射吸收光谱学）和光电子光谱学（x射线光电子光谱学也使用同步辐射，近边缘x射线吸收精细结构），结合其他方法提供这些信息。从超高真空（UHV）的研究开始，我们将通过探索环境压力和液体环境下的锚定反应（漫反射红外傅立叶变换光谱，偏振调制IRAS，近环境压力XPS，电化学红外反射吸收光谱）来弥合理想条件与现实条件之间的差距。此外，我们将直接将特高压实验与在液体环境中进行的反应性研究和光谱学结合起来。funCOS 3提供的关键信息包括反应机理、键的几何形状、能量学、动力学和键形成的可逆性。在第一个资助阶段，我们探索了分子锚定的基本方面，使用简单的模型表面、小测试分子和简单的卟啉衍生物。在此基础上，该项目将采取下一步措施，探索复杂分子、纳米结构表面和现实环境。我们将把注意力从MgO（100）转移到更复杂的氧化钴（Co3O4, CoO）和二氧化钛（TiO2），这是探索从特高压到液体环境中分子锚定的理想测试案例。具体来说，我们将针对五个关键挑战：(1)我们将把知识和方法从小测试分子转移到功能化卟啉衍生物。利用我们在羧酸锚方面的专业知识，我们将调整取代模式，使用多重锚定或使用螯合锚定来控制分子取向，形成动力学和稳定性。(2)探讨水在分子锚定中的作用。从特高压研究开始，确定锚定膜中的质子和OH基团，我们将研究H2O对键形成的影响，最后，将这些研究与环境压力和液体环境下的光谱学联系起来。(3)基于我们对羧酸锚的全面研究，我们将探索调节分子-表面相互作用的替代锚（膦酸、羟肟酸、羟基、儿茶酚）。(4)我们将探索通过取代和金属化（芳香和空间相互作用、极性基团、氢键、金属配位）来独立调节分子间和分子表面相互作用的概念。(5)最后，我们将利用这些知识探索纳米结构氧化物的选择性锚定，例如通过使用锚定与特定表面结构的选择性相互作用。