Radical-containing Porous Organosilica Host Phases Studied by Advanced Electron Paramagnetic Resonance Techniques

通过先进电子顺磁共振技术研究含自由基的多孔有机二氧化硅主相

• 批准号: 429839772
• 负责人: Professor Dr. Michael Fröba
• 金额: --
• 依托单位: Institut für Anorganische und Angewandte Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/429839772?language=en
• 关键词: Radical; containing; Porous; Organosilica; Host

This project is aimed at investigation of a new family of functional nanostructured materials – porous organosilica phases, including periodic mesoporous organosilica (PMO), decorated with stable radicals – using advanced Electron Paramagnetic Resonance (EPR) techniques. Such organosilica phases attract a lot of attention as prospective robust sorbents for small molecules, including gases, and the use of stable radicals attached to the surface of mesoporous materials enhances their functional properties. At the same time, these paramagnetic dopants are excellent signalling molecules for EPR. In particular, adsorption of other paramagnetic and diamagnetic molecules in porous organosilica host phases and the role of stable radicals and interaction with them are of practical interest. Within this project, we propose the synthesis of new radical-labeled porous organosilica host phases, their physicochemical characterization and extensive structural and functional study by EPR. First of all, radical attachment modes and their local surrounding in bare materials will be characterized by continuous wave and pulse multifrequency EPR. Next, adsorption and desorption of various guest molecules including nitric oxide (NO), nitrogen dioxide (NO2), volatile radicals such as TEMPO and others, will be studied in detail. We aim at in-depth understanding of interactions between guest molecules and various radical sites in the pores of organosilica phases, and on elucidation of mechanistic aspects of adsorption. This information becomes available via application of advanced pulse EPR methods such as ENDOR (Electron-Nuclear Double Resonance), HYSCORE (Hyperfine Sublevel Correlation Spectroscopy), DEER/PELDOR (Double Electron-Electron Resonance), etc. The detailed understanding of local structure and function of radical centers in porous organosilica host phases is anticipated as a result of proposed project. This will strongly aid in developing further strategies for directed design of such radical-decorated porous materials for gas separation, storage, sensing, catalytic and other potential applications.

该项目的目的是调查一个新的家庭的功能纳米结构材料-多孔有机硅相，包括周期性介孔有机硅（PMO），装饰稳定的自由基-使用先进的电子顺磁共振（EPR）技术。这样的有机硅相吸引了大量的关注，作为小分子，包括气体的预期鲁棒吸附剂，和使用连接到介孔材料的表面的稳定自由基增强其功能特性。同时，这些顺磁性掺杂剂是EPR的优良信号分子。特别是，吸附的其他顺磁性和反磁性分子在多孔有机硅主机相和稳定的自由基的作用和与他们的相互作用是实际利益。在这个项目中，我们提出了新的自由基标记的多孔有机硅主体相的合成，它们的物理化学表征和广泛的结构和功能的EPR研究。首先，自由基附着模式及其在裸材料中的局部环境将被表征为连续波和脉冲多频EPR。接下来，将详细研究包括一氧化氮（NO）、二氧化氮（NO2）、挥发性自由基如克里思等在内的各种客体分子的吸附和解吸。我们的目标是深入了解客体分子和有机硅相的孔中的各种自由基位点之间的相互作用，并阐明吸附的机理方面。通过应用先进的脉冲EPR方法，如ENDOR（电子-核双共振），HYSCORE（超精细次能级相关光谱），DEER/PELDOR（双电子-电子共振）等，这些信息变得可用的局部结构和功能的自由基中心的多孔有机硅主机相的详细了解预计作为拟议项目的结果。这将有力地帮助开发用于气体分离、储存、传感、催化和其他潜在应用的这种自由基修饰的多孔材料的定向设计的进一步策略。