Control of the formation and reaction of copper-oxygen adduct complexes in multiphase streams

多相流中铜氧加合物的形成和反应的控制

• 批准号: 256729061
• 负责人: Professorin Dr. Sonja Herres-Pawlis
• 金额: --
• 依托单位: Lehrstuhl für Bioanorganische Chemie
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/256729061?language=en
• 关键词: Control; formation; reaction; copper; oxygen

Within the SPP1740, the task of the Herres-Pawlis group was the development of tailored chemical reaction systems. The investigations targeted systems which react with oxygen and nitrogen monoxide for a detailed understanding of the processes in multiphase mixtures, as are present in reactive bubbly flows. Most important requirement is the tunable reaction speed as well as the sensitivity towards different measurement methods in order to probe in space- and time-resolved manner the reaction with the gas. Here, in situ spectroscopic methods are in the focus, e.g. Raman and fluorescence spectroscopy. Six different reaction systems have been developed and investigated towards their kinetic and theoretical aspects by means of stopped-flow spectroscopy, in the super focus mixer and in the Taylor bubble.The goal of the second funding period is to detect multidimensionally the oxygen transfer with subsequent consecutive or parallel reaction with mixing sensitivity and to elucidate the complete kinetics with mass transfer coefficients. Herefore, the system shall be detectable by LIF and be available in large quantities. The special challenge lies in tuning of the systems to room temperature whereby the defined Cu2O2 chemistry normally proceeds at -80°C. This is only possible by sophisticated ligand design. Additionally, strategies for the ligand recycling have to be developed in order to cover the required amounts within the SPP1740. The characterisation of the kinetics of oxygen activation and transfer will be performed by UV/Vis and stopped-flow spectroscopy in order to obtain the intrinsic reaction constants. In collaboration with selected working groups, multidimensional experiments in the super focus mixer, the Taylor-bubble, Taylor-flow, one- and two bubble cells, helical capillary flow reactors up to the bubble column are envisioned: herefore the colour of the generated systems but also their fluorescence response is utilised. A comprehensive kinetic analysis of all steps as well as a deep understanding of the mass transfer through the phase boundary layer gas-liquid is needed for the usage of the oxygenation reactions in technical scale. Here, simulation will aid in all size scales: density functional theory will help to model the atomistic steps of the most promising systems whereas further SPP partners simulate the kinetics in the super focus mixer, the Taylor bubble and the capillary flow reactor. Compared to the first project phase competitive-parallel and consekutive reactions will be studied.

在SPP1740中，Herres-Pawlis小组的任务是开发定制的化学反应系统。研究的目标是与氧气和一氧化氮反应的体系，以详细了解多相混合物中的过程，如反应性泡状流中存在的过程。最重要的要求是可调的反应速度以及对不同测量方法的灵敏度，以便以空间和时间分辨的方式探测与气体的反应。在这里，原位光谱方法是重点，例如拉曼光谱和荧光光谱。在超聚焦混合器和泰勒气泡中，利用停流光谱研究了六种不同的反应体系的动力学和理论。第二个资助期的目标是多维地检测具有混合敏感性的后续连续或平行反应的氧转移，并用传质系数来解释完整的动力学。因此，该系统应可通过激光诱导荧光检测并大量供应。特殊的挑战在于将系统调整到室温，从而定义的Cu2O2化学通常在-80°C进行，这只有通过复杂的配体设计才能实现。此外，还必须制定配体回收战略，以满足SPP1740的要求。氧的活化和转移动力学的表征将通过UV/Vis和停流光谱来进行，以获得本征反应常数。与选定的工作组合作，设想在超级聚焦混合器、泰勒气泡、泰勒流动、一个和两个气泡池、直到鼓泡柱的螺旋毛细管流反应器中进行多维实验：因此，生成的系统的颜色以及它们的荧光响应都被利用。为了在工业规模上使用氧化反应，需要对所有步骤进行全面的动力学分析，并深入了解相边界层气-液之间的传质过程。在这里，模拟将有助于所有规模：密度泛函理论将有助于对最有希望的系统的原子步骤进行建模，而其他SPP合作伙伴将模拟超级聚焦混合器、泰勒气泡和毛细流动反应器中的动力学。与一期工程相比，将研究竞争-平行反应和确信反应。